CN1984969A - Hydrophilic compositions, methods for their production, and substrates coated with such compositions. - Google Patents

Abstract

Liquid compositions are disclosed that include a photocatalytic material and a hydrophilic binder that includes an essentially completely hydrolyzed organosilicate. Also disclosed are methods of making such compositions, methods of coating a substrate with a hydrophilic composition, and substrates coated with such compositions. The compositions may, for example, be embodied as stable one-pack compositions.

Description

Hydrophilic compositions is produced their method and is scribbled the base material of said composition

The cross reference of related application

The application has required the U.S. Provisional Patent Application sequence number No.60/575 of application on May 28th, 2004,437 rights and interests.

Invention field

The present invention relates to comprise the liquid composition that is dispersed in the photocatalyst material in the wetting ability base-material, this base-material comprises basically the organosilicon acid esters of hydrolysis fully.This liquid composition can be particularly as coating composition.Especially, this liquid composition can be as for example stable one package coating compositions, and said composition forms the wetting ability that can demonstrate favourable property easy to clean, self-cleaning property, didirtresistance, fog resistance, antistatic property and/or antibacterium performance and the coating of weather resistance.Can give Superhydrophilic by the photoexcitation of photocatalyst material by the coating that this liquid composition forms.

Background of invention

Hydrophilic coating is favourable for some application, when for example needing to demonstrate the coated surface of didirtresistance, property easy to clean, self-cleaning property and/or anti-fogging performance.This type coating can be particularly useful for, and for example, is applied over the surface that is exposed to outdoor environment.Building structure and other goods that are exposed to outdoor environment touch all contaminations probably, as dirt, and oil, dust and clay etc.For example, rainfall may be carried this pollutant.When rainwater when coated surface flows down, the surface that has deposited hydrophilic coating above can show antifouling property by preventing that pollutent in rainwater is attached on the surface.In addition, at fine day, the pollutent that air carries may contact and be attached to this surface with these surfaces.The surface that deposits hydrophilic coating can be a self-cleaning property because when this surface contact water when (as in rainfall) this coating the ability of washing pollutent off is arranged.

Coating with self-cleaning property and/or antifouling property also can advantageously be applied over and be exposed to for example surface of kitchen pollution thing (as oil and/or fat) of indoor pollutant.The goods that deposited hydrophilic coating can soak in water, come to discharge pollutent and need not to use washing composition just can remove pollutent from the surface of goods from coating with water-wet or with water rinse.

Coating with anti-fogging performance can be used in particular in many application equally.For example, goods with surface that visibility wherein seems important, as windshield glass, window glass, eyeglass lens, reflective mirror and other similar articles can be benefited from the coating with anti-fogging performance, because they usually have by steam or condensate moisture mist that thing is tied or are attached to the fuzzy surface of its lip-deep water droplet.Well-known is that therefore the knot mist of product surface causes airborne around moisture generation condensation and form the condensate moisture thing on the surface of goods remain on the temperature generation of following time lower than the dew point of surrounding environment when this surface.If this condensation product particle is enough little, so that their diameter is when being visible wavelength only about half of, and this particle can cause scattering of light, and the surface obviously becomes opaque thus, causes the loss of visibility.

The surface that has deposited hydrophilic coating can be an anti-fogging, and this is because this type coating can change into the condensation product particle moisture film relatively uniformly, and can not form discrete water droplet.Similarly, the surface that has deposited hydrophilic coating can prevent from rainfall or dabble to form discrete water droplet from the teeth outwards, has improved the visibility of passing window, reflective mirror and/or glasses thus.

Consider these and other advantage, advised various hydrophilic coating compositions already.In these coating some are by being dispersed in the wetting ability that is used for realizing them of the photocatalyst material in the siliceous base-material.For example, U.S. Patent No. 5,755,867 (" ' 867 patents ") disclose the particulate state photocatalyst that is dispersed in the coating formation usefulness composition.Photocatalyst preferably is made up of the titanium dioxide granule with 0.1 micron or lower median size, and wherein titanium dioxide can use with the form of Detitanium-ore-type or rutile-type.Coating formation can form the coating of silicone resin with composition and be made up of the partial hydrolysis of hydrolyzable silane, the formed organopolysiloxane of polycondensation subsequently when solidifying.In ' 867 patents, polysiloxane coating forms has sizable hydrophobicity with composition itself, and still by the exciting of dispersive photocatalyst, can give this water affinity that is coated with layer height is wetting ability.

Japanese patent application JP-8-164334A discloses to film to form and has used composition, and it comprises the hydrolysate and the solvent of the titanium dioxide of the median size with 1-500 nanometer, hydrolyzable silicon compound.Hydrolyzable silicon compound is by general formula SinO _N-1(OR) _2n+2(wherein n is that 2-6 and R are C to the alkyl silicate condenses of expression ₁-C ₄Alkyl).This hydrolysate obtains with the hydrolysis percentage hydrolysis alkyl silicate condenses of 50-1500%.Yet this hydrolysate itself is not considered to hydrophilic.

US Patent No 6,013,372 and 6,090,489 disclose light-catalysed coating composition, wherein the particle of photocatalyst be dispersed in uncured or partly solidified polysiloxane (organopolysiloxane) or its film forming component of precursor in.Photocatalyst can comprise the particle of metal oxide, as the anatase octahedrite and the rutile form of titanium dioxide.According to these patents, the composition that coating composition is applied on the surface of base material and film forming is used is cured then.Then, by the photoexcitation of photocatalyst, be bonded in film forming and under the photocatalysis of photocatalyst, replaced by hydroxyl with the organic group on the Siliciumatom of the polysiloxane molecule of composition.The surface of photocatalysis coating is " super hydrophilization " thus, and promptly the surface is endowed highly hydrophilicly, makes contact angle with water become and is lower than about 10 °.Yet in these patents, film forming is significantly hydrophobic with composition itself, that is, with the initial contact angle of water greater than 50 °.As a result, coating is hydrophobic at first, and only just makes the coating possess hydrophilic property by exciting of dispersive photocatalyst.

U.S. Patent No. 6,165,256 disclose the surface hydrophilic that can make element so that give the composition of anti-fogging performance for element surface.Disclosed composition comprises the photocatalytic particle of (a) metal oxide in this patent, and the precursor that (b) can form silicone resin film maybe can form the precursor of silica film and (c) solvent, as water, organic solvent and their mixture.Solvent is so that the total content of the solid matter of photocatalytic particle and precursor in composition is the amount interpolation of 0.01-5% (by weight).Yet the same with the example of front, the hydrophilization of the coating that forms from said composition is that the photoexcitation by photocatalyst takes place, and film forming is not hydrophilic with material itself simultaneously.Therefore, before the exciting of photocatalyst, it is hydrophilic that this type coating is not considered to.

Yet, by be dispersed in photocatalyst material in the siliceous base-material be used for realize that there are some defectives in hydrophilic these prior art hydrophilic coatings of coating.A remarkable shortcoming is that these coatings did not demonstrate wetting ability before the photoexcitation of photocatalyst.In addition, these compositions typically need to force curing, that is, they at room temperature can not solidify effectively.

U.S. Patent No. 6,303,229 (" ' 229 patents ") disclose the another kind of composition that can comprise photocatalyst material.The coating that is disclosed in this ' 229 patent forms by applying the coating composition that contains silicone resin, and this silicone resin obtains as base-material and by hydrolysis and some four functionalized organoalkoxysilane of polycondensation.Coating composition also can comprise colloided silica.Significantly, formed the filming of the composition from be disclosed in this ' 229 patent can be hydrophilic at first.Yet these initial wetting abilities it is believed that it is that the existence of colloided silica in composition causes, rather than silicone resin itself possesses.It is believed that the silicone resin itself that is disclosed in this ' 229 patent is not hydrophilic, because desirable resin pH is 3.8-6, this shows that the Si-OR group is present in the resin to prevent gelation and hydrophilic amount.As a result, there are some defectives in this type coating.For example, if at this base material and contain between the coating composition of silicon resin and do not comprise undercoat, comprise that this type of coating of photocatalyst material can not directly be applied on organic class material effectively.In addition, when composition is applied on the organic substrate with bigger film thickness, in coating composition, comprises colloided silica and will cause iris.

As a result, advantageously provide the composition that comprises photocatalyst material and base-material, wherein the coating that is formed by said composition was hydrophilic before the exciting of photocatalyst and can becomes Superhydrophilic by exciting of photocatalyst.Such one type composition is provided also advantageously, and it has low haze, can solidify efficiently at ambient temperature, and/or can keep their wetting ability for a long time when being exposed to dark state.In addition, advantageously use said composition with stable single wrapped product form.

The accompanying drawing summary

Fig. 1 is the figure that the Fourier transform infrared spectrophotometric spectra (" FTIR ") that reflected the dry film that is formed by the wetting ability base material according to some non-limiting embodiments of the present invention is analyzed;

Fig. 2 is the schematic cross-sectional view of the magni-scale of some non-limiting embodiments of the present invention; With

Fig. 3 is a field-emission scanning electron microscope secondary electron Photomicrograph (amplifying 40,000 times) of having described some non-limiting embodiments of the present invention.

Fig. 4 is the figure that has illustrated according to the result of the endurance test of carrying out in method described in the embodiment 2.

Summary of the invention

In one aspect, the present invention relates to liquid composition, as coating composition, it comprises (a) photocatalyst material and (b) base-material.The base-material of composition of the present invention is hydrophilic and comprises the organosilicon acid esters of hydrolysis fully basically.

In yet another aspect, the present invention relates to make the method for this type of liquid composition (single packed liq composition), with the method for this liquid composition coated substrate, and the base material that scribbles liquid composition of the present invention.

The detailed description of invention embodiment

For following detailed description, be understood that the present invention can suppose various alternative versions and sequence of steps, unless opposite regulation is clearly arranged.And except in any operation embodiment, or when indicating in addition, otherwise the whole numerical value that for example are used for expressing the amount of the composition that uses in specification sheets and claim are interpreted as being modified by term " about " in all instances.Therefore, unless opposite indication is arranged, otherwise the numerical parameter that provides in specification sheets below and the claims is the desired properties that can be obtained according to the present invention change approximate.At least, and do not attempt the application of doctrine of equivalents is limited to the scope of claim, each numerical parameter should be at least according to the numerical value of the significant figure of report and adopt the ordinary technology of rounding off to explain.

Although it is proximate expressing the numerical range and the parameter of wide region of the present invention, the numerical value that provides is in a particular embodiment reported as far as possible exactly.Yet any numerical value contains some error that standard deviation certainly led to of finding by in their experimental measurements separately inherently.

In this application, the use of odd number comprises that plural number and plural number comprise odd number, unless specify in addition.For example and without limits, the application mentions the liquid composition that comprises " photocatalyst material ".Quote for " photocatalyst material " this and to be meant the composition that comprises a kind of photocatalyst material and to comprise composition, as comprise the composition of two kinds of different photocatalyst materials more than a kind of photocatalyst material.In addition, in this application, " or " use be meant " and/or ", unless specify in addition, although " and/or " can use in some cases clearly.

Equally, it should be understood that any numerical range of listing is intended to comprise the whole subranges that are included in wherein here.For example, the scope of " 1-10 " is intended to be included in whole subranges of (and comprising end value) between cited minimum value 1 and the cited maximum value 10,, has minimum value that is equal to or greater than 1 and the maximum value that is equal to or less than 10 that is.

The present invention relates to liquid composition, as coating composition, it comprises (a) photocatalyst material and (b) base-material.The base-material of composition of the present invention is hydrophilic and comprises the organosilicon acid esters of hydrolysis fully basically.

Liquid composition of the present invention comprises photocatalyst material.Here the term of Shi Yonging " photocatalyst material " refers to by being exposed to the material that radiation (as ultraviolet ray or visible radiation) and absorbing radiation can photoexcitations.Photocatalyst material is a kind of like this material, and when being exposed to energy than higher light time of energy gap between crystalline conduction band and valence band, it causes exciting of the electronics that is in the valence band, thereby produces conduction and stay the hole on this specific valence band.In certain embodiments of the invention, this photocatalyst material comprises metal oxide, as zinc oxide, and stannic oxide, ferric oxide, bismuthous oxide bismuth trioxide, tungstic oxide, strontium titanate, titanium dioxide, or their mixture.

In certain embodiments of the invention, at least a portion of photocatalyst material is present in the liquid composition with the particle form of the average crystal diameter of 1-100 nanometer, as the 3-35 nanometer, or, in another other embodiment, the 7-20 nanometer.In these embodiments, the particulate average crystal diameter can be between any combination of cited value, comprises cited value.It will be understood by those skilled in the art that the performance that the particulate average crystal diameter can be incorporated in the liquid composition with hope is that the basis is selected.In some embodiments, whole basically photocatalyst materials exist with this type of particulate form.The average crystal diameter of photochemical catalysis metal oxide particle can be measured and this type of particulate crystallization phases can be measured by X-ray diffraction by scanning electronic microscope or transmission electron microscope, and is such as is known to persons skilled in the art.

As mentioned above, they can photochemical catalysis by being exposed to for example ultraviolet ray (" UV ") and/or visible radiation and absorption for some material.In certain embodiments of the invention, photocatalyst material comprises and can carry out the material of photoexcitation by in these mechanism one or more.Can be used for the present invention and light-catalysed examples of material comprises by being exposed to ultraviolet radiation, without limits, stannic oxide, zinc oxide, and the brookite of titanium dioxide, anatase octahedrite and rutile form.Can be used for the present invention and light-catalysed examples of material comprises by being exposed to visible radiation, without limits, the brookite form of titanium dioxide is carried out the titanium dioxide of chemical modification via the flame pyrolysis of metal titanium, the titanium dioxide of adulterated titanium dioxide of nitrogen and Cement Composite Treated by Plasma.

In certain embodiments of the invention, this photocatalyst material provides with the particulate solation (as the TiO 2 sol form) that comprises the photocatalyst material that is dispersed in the water.This type of colloidal sol is commercially available easily from market.The examples of material that is suitable among the present invention comprises, without limits, can be from the S5-300A and the S5-33B of Millenium Chemicals acquisition, can be from the STS-01 of Ishihara Sangyo Corporation acquisition, STS-02, and STS-21, and can be from NTB-1, NTB-13 and the NTB-200 of Showa Denko Corporation acquisition.

In certain embodiments of the invention, this photocatalyst material exists with the form of the colloidal sol that comprises the brookite type titanium dioxide particle that is dispersed in the water or brookite type and Detitanium-ore-type and/or rutile titanium dioxide particulate mixture.This type of colloidal sol can prepare by titanium tetrachloride hydrolysis under certain condition, as by U.S. Patent No. 6,479, and 031 instruction, it is hereby incorporated by reference.The colloidal sol that is suitable for this type among the present invention comprises, without limits, and the NTB-1 and the NTB-13 TiO 2 sol that can be purchased from Showa Denko Corporation.

In certain embodiments of the invention, this photocatalyst material comprises chemical modification titanium dioxide.This type of examples of material comprises by people such as Khan, Efficient PhotochemicalWater Splitting by a Chemically Modified n-TiO ₂ScienceReprint, 297 volumes, the flame pyrolysis method (document is hereby incorporated by reference) that 2243-2245 page or leaf (2002) is described carries out the titanium dioxide of chemical modification, according at U.S. Patent application publication 2002/0169076 A1, the nitrogen-doped titanium dioxide (document is hereby incorporated by reference) of the method manufacturing of in for example paragraph [0152] to [0203], describing and/or in U.S. Patent No. 6,306, the titanium dioxide (document is hereby incorporated by reference) of the Cement Composite Treated by Plasma of describing in the 49th row-Di 7 hurdles, 343, the 2 hurdles the 17th row.

In certain embodiments of the invention, the amount of the photocatalyst material that exists in liquid composition is the 0.05-5wt% solid, and as the 0.1-0.75wt% solid, wherein the wt% solid is based on total solution weight of composition.The amount of the photocatalyst material that exists in liquid composition in these embodiments, can be between any combination of the above value of enumerating (comprising cited value).The amount that it will be understood by those skilled in the art that the photocatalyst material that exists in liquid composition decides by the performance that hope is incorporated in the composition.

Liquid composition of the present invention also comprises the wetting ability base-material.Here the term of Shi Yonging " base-material " refers to continuous material, wherein is dispersed with the particle of photocatalyst material.Here the term of Shi Yonging " wetting ability base-material " refers to that this base-material itself has affinity for water.The hydrophilic a kind of method of evaluating material be measure water with from the contact angle between the dry film of this material formation.In certain embodiments of the invention, base-material comprises can forming to demonstrate and is no more than 20 ° water contact angle, or in other embodiments, be no more than 15 ° water contact angle, or, in another other embodiment, be no more than the material of dry film of 10 ° water contact angle.

The result, in certain embodiments of the invention, by liquid composition being applied on the base material and follow-up drying, resulting film demonstrated before the photoexcitation of photocatalyst material and is no more than 20 ° water contact angle, be no more than 15 ° in some embodiments, or, be no more than 10 ° in another other embodiment.Here Bao Dao water contact angle be by water droplet measure at the tangent line of the water droplet shape on the point of contact and the observed value of the angle between the substrate surface, and by using by Lord Manufacturing, Inc. that make, that GaertnerScientific protractor optics is housed modified version is caught bubble (captive bubble) telltale, measures by stopping dripping method (sessile drop).The surface that will measure is placed on level attitude, towards last, in the front of light source.The water that will stop to drip is placed on the top on surface of light source front, and contact angle (pressing the number of degrees) be observed and be measured to the profile that stops like this to drip can by the graduated protractor farsighted glasses of circular protractor is housed.

In certain embodiments of the invention, this liquid composition comprises the base-material that demonstrates antistatic property, that is, this base-material can form can dissipation of static charge dry film.It will be recognized by those skilled in the art that a kind of mode of analyzing the antistatic effect of this material is to measure the surface resistivity of material.In certain embodiments of the invention, base-material comprises the material that can form dry film, and this film demonstrates 7.5 * 10 ⁹To 1.5 * 10 ¹²Ohm/cm ², or, in other embodiments, be no more than 1.0 * 10 ¹⁰Ohm/cm ²Surface resistivity.Here Bao Dao surface resistivity can be used ACL Statitide Model 800 Megohmeter, by using (1) big elongated probe of 5 millimeters at interval on the several position on the sample, or (2) on the several position on the sample at interval probe on the plate of this instrument of 2.75 inches measure.As a result, the invention still further relates to liquid composition with this type of antistatic property.

Liquid composition of the present invention comprises base-material, and this base-material comprises basically the organosilicon acid esters of hydrolysis fully.Here the term of Shi Yonging " organosilicon acid esters " refers to contain the compound that is bonded in the organic group on the Siliciumatom by Sauerstoffatom.Suitable organosilicon acid esters comprises, without limits, contains by Sauerstoffatom and is bonded in the organic radical TMOS of four organic groups on the Siliciumatom and has the siloxane main chain ((Si-O) that is made of Siliciumatom _n) organic radical oxygen radical siloxane.

In the organosilicon acid esters pass through Sauerstoffatom be bonded on the Siliciumatom organic group without limits and can comprise, for example linear, branching or cyclic alkyl.The specific examples that Sauerstoffatom is bonded in the organic group on the Siliciumatom of passing through in the organosilicon acid esters comprises, without limits, and methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, hexyl, octyl group or similar group.Among these alkyl, usually use C ₁To C ₄Alkyl.The example of other suitable organic group comprises aryl, xylyl, naphthyl or the like.This organosilicon acid esters can contain two or more dissimilar organic groups.

The specific non-limitative example of suitable organic radical TMOS is a tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, tetraisobutoxy-silicane alkane, four sec-butoxy silane, four tert.-butoxy silane, tetraphenoxy-silicane alkane and dimethoxy diethoxy silane.These organosilicon acid esters can use separately or use with any two or more binding substances among them.Among these organosilicon acid esters, the condenses of tetramethoxy-silicane and/or its partial hydrolysis demonstrates high hydrolytic reactivity and therefore can easily produce silanol group.

The specific non-limitative example of suitable organic radical oxygen radical siloxane is the condenses of above organic radical TMOS.The condensation degree of organic radical oxygen radical siloxane is restriction especially not.In certain embodiments, this condensation is in the scope that is expressed from the next:

SiO _x(OR) _y

Wherein x be 0 to 1.2 and y be 1.4 to 4, precondition is that (2x+y) is 4; With R be organic group, as C ₁-C ₄Alkyl.

This coefficient or subscript x represent the condensation degree of siloxanes.When this siloxanes showed molecular weight distribution, this coefficient x referred to average condensation degree.The compound of being represented by the above general formula of x=0 wherein is as monomeric organic radical TMOS class and the corresponding oligopolymer of condenses that is and obtained by the partial hydrolysis condensation reaction by the compound that the above general formula of 0＜x＜2 is wherein represented.Simultaneously, the compound of being represented by the above general formula of x=2 wherein is corresponding to SiO ₂(silica).In certain embodiments, the condensation degree x that is used for the present invention's organosilicon acid esters is 0 to 1.2, in 0 to 1.0 scope.This siloxane main chain can have linear, branching or ring texture or their mixture.Above general formula: SiO _x(OR) _yCan pass through in U.S. Patent No. 6,599,976, the 5 hurdles, the Si-NMR that describes in the 10th to 41 row measures, and the document is hereby incorporated by reference.

As previously mentioned, the base-material of liquid composition of the present invention comprises basically the organosilicon acid esters of hydrolysis fully.Here the term of Shi Yonging " the organosilicon acid esters of hydrolysis fully basically " refers to a kind of like this material, wherein the organic radical oxygen base of organosilicon acid esters is substituted into by silanol group basically and makes this material become hydrophilic degree, promptly, this material can form dry film, and this dry film demonstrates and is no more than 20 ° water contact angle, or in other embodiments, be no more than 15 ° water contact angle, or, in another other embodiment, be no more than 10 ° water contact angle.This hydrolysis can produce network polymer, as following illustrated:

Wherein m and n are that positive number and m are not more than n.In certain embodiments of the invention, the organic silicic acid ester of hydrolysis fully is substantially free of-the OR group basically, is recorded by FTIR or other suitable analysis technology.

Referring now to Fig. 1,, can see the figure of the FTIR analysis that has reflected the dry film that forms by this class wetting ability base material.Can clearly be seen that, on Si-OH key wave number (it is 920-950) and Si-O-Si key wave number (it is 1050-1100), observe tangible peak.On the other hand, can clearly be seen that film is substantially free of-the OR group, wherein R represents C ₁-C ₄Alkyl, this can confirm by the disappearance at any significant peak on Si-OR wave number (it is 2900-3000).

In certain embodiments, the organosilicon acid esters that is included in the hydrolysis fully basically in the base-material of the present invention is the product of organosilicon acid esters with the hydrolysis of a large amount of water in the presence of the acid hydrolysis catalyzer.This hydrolysis can be carried out in order to the water that exists greater than a kind of amount of the stoichiometric amount of organic radical oxygen base that can this organosilicon acid esters of hydrolysis significantly.The interpolation that it is believed that this excessive water makes and to be existed simultaneously by the silanol group that hydrolysis produced of organosilicon acid esters and a large amount of water, prevents the condensation reaction of silanol group thus.

The hydrolysis of organosilicon acid esters can be carried out in the presence of one or more acid hydrolysis catalyzer.The specific examples of suitable catalyst comprises, without limits, and mineral acid, example hydrochloric acid especially, sulfuric acid, nitric acid and phosphoric acid; Organic acid, especially as acetate, Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, phenylformic acid, phthalic acid, toxilic acid, formic acid, citric acid, and oxalic acid; Basic catalyst, as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia; And organic amine compound, organometallic compound except that this organosilicon acid esters or metal alkoxide thing, for example, organo-tin compound, as dibutyl tin dilaurate, two sad dibutyl tin and dibutyltin diacetates, organo-aluminium compound, as three (acetopyruvic acid) aluminium, two (ethylacetoacetone(EAA,HEAA) acid) aluminium of single acetyl pyruvic acid, three (ethylacetoacetone(EAA,HEAA) acid) aluminium and ethylacetoacetone(EAA,HEAA) acid aluminium diisopropyl hydrochlorate, organic titanic compound, as four (acetopyruvic acid) titanium, two (butoxy)-two (acetopyruvic acid) titaniums and four titanium n-butoxide, and organic zirconate, as four (acetopyruvic acid) zirconium, two (butoxy)-two (acetopyruvic acid) zirconium, (isopropoxy)-two (acetopyruvic acid) zirconiums and four n-butoxy zirconiums, and boron compound, as three n-butoxy boron and boric acid; Or the like.

In certain embodiments, be used for also can comprising organic solvent outside base-material dewaters, as alcohols, diol, derivatives, hydrocarbon, ester, ketone, ether or the like.These solvents can use separately or use with any two or more mixture among them.

The specific examples of operable alcohols comprises, without limits, and methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, methyl ethyl diketone alcohols or the like.The specific examples of operable diol, derivatives comprises, without limits, and ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol list ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate or the like.The specific examples of operable hydrocarbon comprises, without limits, and benzene, toluene, dimethylbenzene, kerosene, normal hexane or the like.The specific examples of operable ester comprises, without limits, and methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl acetoacetate, methyl aceto acetate, butyl-acetoacetate or the like.The specific examples of operable ketone comprises acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Acetyl Acetone or the like.The specific examples of operable ether comprises, without limits, and ether, butyl ether, methyl cellosolve, ethoxy ethanol, two _ alkane, furans, tetrahydrofuran (THF) or the like.

The base-material and their production method that are suitable among the present invention are described in U.S. Patent No. 6,599, and 976, the 3 hurdles, the 57th row are to the 10th hurdle, and in the 58th row, it is hereby incorporated by reference.The organosilicon acid esters and the non-limitative example that is purchased material that be suitable for the base-material in the composition of the present invention that belongs to hydrolysis fully basically is can be from Mitsubishi Chemical Corporation, Tokyo, the MSH-200 that Japan obtains, MSH-400 and MSH-500 silicon ester, with can be from Dainippon Shikizai, Tokyo, the Shinsui Flow MS-1200 silicon ester that Japan obtains.

In certain embodiments, this base-material prepares in multistage process, wherein organic radical TMOS (as previously mentioned in those any) and water react in the presence of acid hydrolysis catalyzer (as previously mentioned in those any) in the fs, and wherein the amount of water is lower than the stoichiometric amount of organic radical oxygen base that can hydrolysis organic radical TMOS.In certain embodiments, this acid hydrolysis catalyzer comprises organic acid.In certain embodiments, water exists with 50% stoichiometric amount of organic radical oxygen base that can hydrolysis organic radical TMOS in the fs.The result of fs is the partial hydrolysis polycondensation product.

In certain embodiments, the multistage base-material preparation technology fs in restriction owing to carry out under the condition of the condensation degree of the formed Si-OH group of hydrolysis reaction.This type of condition can comprise, for example, controls exothermic heat of reaction by for example exterior cooling, and the speed of acid catalyst is added in control, and/or carries out the fs hydrolysis under the situation that does not have (or not existing fully) any organic cosolvent basically.

In subordinate phase, the partial hydrolysis polycondensation product contacts with a large amount of water then, usually under the situation that does not have the acid hydrolysis catalyzer.The water yield of in subordinate phase, using significantly greater than (" significantly greater than " be meant gained solution contains be not more than 2% solid) can hydrolysis organic radical TMOS the stoichiometric amount of organic radical oxygen base.

In another other embodiment, base-material is from the initial preparation of tetraalkoxysilane oligopolymer, as from Mitsubishi Chemical Corp. with trade name MKC Silicate MS-51, MKC Silicate MS-56 and MKC Silicate MS-60 (all are trade mark; The product of Mitsubishi Chemical Corp) those that are purchased.This quasi-oligomer and water react in the presence of organic acid hydrolyst (for example acetate) and/or organic solvent, and wherein the amount of water is significantly greater than the stoichiometric amount of organic radical oxygen base that can the hydrolysis tetraalkoxysilane.

As a result, the invention still further relates to the method for the hydrophilic compositions of making the organosilicon acid esters that comprises basically hydrolysis fully.The embodiment has here described the exemplary condition of these class methods.

The amount of the organosilicon acid esters that exists in liquid composition in certain embodiments of the invention, is with the SiO in the organosilicon acid esters ₂Count 0.1-2wt%, as 0.2-0.90wt%, based on the gross weight of composition.In these embodiments, the amount of the organosilicon acid esters that exists in liquid composition can be between any combination of the above value of enumerating, and comprises cited value.The amount that it will be understood by those skilled in the art that the organosilicon acid esters that exists in liquid composition decides by the performance that hope is incorporated in the composition.

In certain embodiments of the invention, this photocatalyst material and organosilicon acid esters were with 0.05: 0.95 to 5: 0.3 (by weight), or, 0.10: 0.90 to 3.0: 0.5 (by weight) in other embodiments, or in another other embodiment, the ratio of at least 0.3: 0.5 (by weight) or 0.2: 0.6 (by weight) is present in the liquid composition.In these embodiments, the ratio of photocatalyst material and organosilicon acid esters can comprise cited value between any combination of cited value.It will be appreciated by those skilled in the art that, the ratio of photocatalyst material and organosilicon acid esters is incorporated into performance in the composition by hope in liquid composition, decides as the desired refractive index that has of composition (it is by deciding with reference to the base material that applies composition).

In certain embodiments, liquid composition of the present invention can further comprise inorganic particle, silica for example, alumina, comprise and handle alumina (for example silica-processing alumina is called αYang Hualv) interior, silicon carbide, diamond powder, cube shaped boron nitride, and norbide.This type of inorganic particle can for example be colourless basically, as silica, and colloided silica for example.This type of material can provide enhanced mar-proof and anti-zoned property.This type of particle can have from submicron (for example nano-sized particles) to 10 microns mean particle sizes, and this depends on the final application and the desired effect of composition.

In certain embodiments, in being introduced in liquid composition before, this particle comprises having from 1 to 10 micron, or the inorganic particle of from 1 to 5 micron mean particle size.In other embodiments, in being introduced in liquid composition before, this particle can have from 1 nanometer to being lower than 1000 nanometers, to 100 nanometers, or in certain embodiments, 5 nanometers are to the mean particle size between 50 nanometers as 1 nanometer.In some embodiments, in being introduced in liquid composition before, this inorganic particle has the 5-50 nanometer, or the mean particle size of 5-25 nanometer.Granularity can comprise this enumerator between any combination of these values.

In certain embodiments of the invention, this particle can be with 5.0wt% at the most, or from 0.1-1.0wt%; Or be present in the liquid composition from the amount of 0.1-0.5wt%, based on the gross weight of composition.The particulate amount that exists in liquid composition can comprise this enumerator between any combination of these values.

In certain embodiments of the invention, this liquid composition also comprises antimicrobial strongthener, for example metal; As silver, copper, gold, zinc, their compound, or their mixture; Quaternary ammonium compound, as benzalkonium chloride, dialkyl dimethyl ammonium chloride, cetyl trimethylammonium bromide, cetylpyridinium chloride, and 3-(trimethoxysilyl)-propyl-dimethyl-octadecyl-ammonium chloride; Phenols, as 2-benzyl-chlorophenol, orthoxenol, neighbour-phenylphenol sodium, pentachlorophenol, 2 (2 ', 4 '-dichlorophenoxy)-5-chlorophenols and 4-chloro-3-methylphenol; Halogen compounds is as TCCA (Trichloroisocyanuric acid) salt, dichloroisocyanuric acid sodium, DCCK, single TCCA (Trichloroisocyanuric acid) salt, DCCK, 1: 4 dichlorodimethylhydantoin, bromo-chloro-dimethyl hydantoin, 2,2 '-two bromo-3-nitrilo propionic acid amides, two (1,4-acetobrom oxygen base)-2-butylene, 1,2-two bromo-2,4-dicyanobutane, 2-bromo-2-nitropropane-1,3-glycol and bromoacetic acid benzyl ester; Organometallic compound, as 10, the two phenoxy group arsines of 10 '-oxo, tributyl tin oxide compound, tributyl tin fluorochemical, copper 8-quinolinolate, copper naphthenate, chromated copper arenate, arsenic acid cuprammonium, and Red copper oxide; Organosulfur compound, as methylene-bis thiocyanic ester (MBT), vinylidene Rhodan ester, chlorethylidene Rhodan ester, Sodium dimethyldithiocarbamate 40min, ethylenebis dithiocarbamic acid disodium, ziram and two (trichloromethyl) sulfone; Heterocyclics, as tetrahydrochysene-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thioketones (DMTT), pyrrole thioketones sodium, pyrrole thioketones zinc, 1, the 2-benzisothiazole-3-ketone, 2-(n-octyl)-4-isothiazoline-3-ketone, 2-(4-thiazolyl) benzoglyoxaline, N-(trichloromethyl sulfenyl)-4-tetrahydrobenzene-1,2-dicarboximide, N-(trichloromethyl sulfenyl)-phthalic imidine and 5-chloro-2-methyl-4-isothiazoline-3-ketone 2-methyl-4-isothiazoline-3-ketone; And nitrogen compound, as N-cocounut oil alkyl trimethylene diamines, N-[α-(1-nitro-ethyl) benzyl]-quadrol, 2-(methylol) amino-ethanol, 2-(methylol) amino-2-methyl propyl alcohol, 2-methylol-2-nitro-1, ammediol, six hydrogen-1,3,5-three-(2-hydroxyethyl)-s-triazine, six hydrogen-1,3,5-triethyl-s-triazine, 4-(2-nitro butyl) morpholine+4,4 '-(2-ethyl-2-nitro-trimethylene)-dimorpholine, glutaraldehyde, 1,3-dihydroxymethyl-5,5-dimethyl-glycolylurea, and Imidurea and their mixture.

Liquid composition of the present invention for example can contain the biocide of the consumption of the effect that is enough to demonstrate opposing microorganism and various especially Mycophytas.More particularly, embodiment of the present invention can contain the biocide that is enough to be suppressed at the consumption of microorganism growth on the base material, according to MTCC (American Association of Chemists﹠amp; Colorists) test method 30, Part III test.Those skilled in the art are familiar with this test method and its parameter.In certain embodiments of the invention, the amount of the microbial resistance strongthener that exists in liquid composition is based on the 0.01-1.0wt% of composition total weight, as 0.1-1.0wt%, or in other embodiments, 0.1-0.5wt%.In these embodiments, the amount of the resistance to bacteria strongthener that exists in liquid composition can comprise cited value between any combination of the above value of enumerating.The amount that it will be understood by those skilled in the art that the resistance to bacteria strongthener that exists in liquid composition decides by the performance that hope is incorporated in the composition.

In certain embodiments, liquid composition of the present invention can comprise the optical activity toughener, as platinum, and gold, palladium, iron, nickel, or its soluble salt.The known redox active that can strengthen photocatalyst of the interpolation of these materials in comprising the composition of photocatalyst material promotes to be attached to the decomposition of the pollutent on the coatingsurface.In certain embodiments of the invention, the amount of the optical activity toughener that exists in liquid composition is based on the 0.01-1.0wt% of composition total weight, as 0.1-1.0wt%, or in other embodiments, 0.1-0.5wt%.In these embodiments, the amount of the optical activity toughener that exists in liquid composition can comprise cited value between any combination of the last value of enumerating.The amount that it will be understood by those skilled in the art that the optical activity toughener that exists in liquid composition decides by the performance that hope is incorporated in the composition.

In certain embodiments, liquid composition of the present invention can comprise coupling agent, and the latter for example improves the adhesivity of composition of the present invention to the japanning base material.The example that is suitable for the coupling agent in the liquid composition of the present invention comprises, without limits, is described in U.S. Patent No. 6,165,256, the 8 hurdles, and the 27th goes to the 9th hurdle, the material in the eighth row, this patent is hereby incorporated by reference.

In certain embodiments of the invention, the amount of the coupling agent that exists in liquid composition is 0.01-1wt%, as 0.01-0.5wt%, based on the gross weight of composition.In these embodiments, the amount of the coupling agent that exists in liquid composition can comprise cited value between any combination of the above value of enumerating.The amount that it will be understood by those skilled in the art that the coupling agent that exists in liquid composition decides by the performance that hope is incorporated in the composition.

In certain embodiments, liquid composition of the present invention can comprise tensio-active agent, and when composition was applied on the coated substrate (as scribbling the base material of organic coating), this tensio-active agent can for example assist to improve the wettability of composition especially.The example that is suitable for the tensio-active agent among the present invention comprises, without limits, and in U.S. Patent No. 6, the 610,777, the 37th hurdle, the 22nd row is to the 38th hurdle, the 60th row and U.S. Patent No. 6,657,001, the 38th hurdle, 46 go to the 40th hurdle, the material of determining in 39 row, and the both is hereby incorporated by reference.

In certain embodiments of the invention, the amount of the tensio-active agent that exists in liquid composition is the 0.01-3wt% based on the composition total solid weight, as 0.01-2wt%, or in other embodiments, 0.1-1wt%.In these embodiments, the amount of the tensio-active agent that exists in liquid composition can be between any combination of the above value of enumerating, and comprises cited value.The amount that it will be understood by those skilled in the art that the tensio-active agent that exists in liquid composition is to decide by the performance that hope is incorporated in the composition.

In certain embodiments, liquid composition of the present invention can comprise cleaning combination.Suitable cleaning combination comprises some materials like this, and the latter comprises tensio-active agent, solvent system, water and pH regulator agent, as acetate or ammonia.Suitable cleaning combination has been disclosed in U.S. Patent No. 3,463, and in 735, it discloses the cleaning combination that comprises solvent system, and this solvent system comprises low boiling point solvent, as Virahol and middle high boiling solvent, as has the C of 3-8 carbon atom altogether ₁-C ₄The aklylene glycol alkyl oxide.Suitable be purchased that cleaning combination comprises can be from SC Johnson and Son, the WINDEX_ that Inc. is purchased.The contriver has been found that when being applied over painted surface, coats sash as aluminium, when aluminum wallboard or the like is gone up, comprises the wettability that cleaning combination can improve said composition in certain embodiments of the invention.As a result, in certain embodiments, before applying liquid composition of the present invention, painted surface needn't clean.

Therefore, certain embodiments of the present invention relate to liquid composition, comprise (a) cleaning combination and (b) the organosilicon acid esters of hydrolysis fully basically.This based composition also can comprise photocatalyst material as previously described.

In certain embodiments, this cleaning combination is with 10wt% at least, and as 20wt% at least, or the amount of 25wt% is present in the liquid composition of the present invention at least in some cases, and wherein wt percentage ratio is based on the gross weight of this liquid composition.

If necessary, coating composition can be included in technical field of coatings other optional coating material known to the skilled.

The invention still further relates to the method for making liquid composition.According to some method of the present invention, this liquid composition is prepared as follows: the water wetted material of the organosilicon acid esters that comprises basically hydrolysis fully (a) is provided, and wherein the pH of water wetted material is no more than 3.5; (b) provide and comprise colloidal sol or the slurry that is dispersed in the photocatalyst material in the thinner, wherein the pH of colloidal sol is no more than 3.5; (c) water wetted material that will provide in (a) mixes so that photocatalyst material is dispersed in the water wetted material with colloidal sol that provides in (b) or slurry.Have been found that the liquid composition that makes by this method can stablize 12 months and do not have coalescent or the precipitation.Here Bao Dao pH value can use the ACCUMET pH meter that is purchased from Fisher Scientific to measure.

Some method of the present invention comprises the step of the water wetted material that the organosilicon acid esters that comprises basically hydrolysis fully is provided, wherein the pH of hydrophilic material is no more than 3.5, in some embodiments, be 1.3 to 3.5, or in another other embodiment, be 3.0 to 3.5.In some embodiment of method of the present invention, this hydrophilic material is by at first providing the material of the organosilicon acid esters that comprises basically hydrolysis fully, wherein the pH of this material is greater than required pH, then acid is added to the pH until this material is no more than 3.5 in this material, or be 1.3 to 3.5 in some practical solution, or in another other embodiment, be till 3.0 to 3.5 and final the acquisition.For example, as previously mentioned, this hydrophilic material can comprise MSH-200 and/or MS-1200 silicon ester, and both are typically provided under 3.5 to 4.5 pH by supplier for they.

In some embodiment of method of the present invention, before adding acid, this hydrophilic material can be used thinner such as water or organic solvent diluting, for example reduces the solids content of hydrophilic material, allows thus to form thin film, and is as described below.

The acids of regulating its pH in the hydrophilic material be can add to and mineral acid and organic acid comprised.Suitable inorganic acid especially comprises, without limits, and hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.Suitable organic acid especially comprises acetate, dichloro acetic acid, trifluoroacetic acid, Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, phenylformic acid, phthalic acid, toxilic acid, formic acid and oxalic acid.

Some method of the present invention comprises providing and comprises the colloidal sol that is dispersed in the photocatalyst material in the thinner or the step of slurry, wherein the pH of colloidal sol or slurry is no more than 3.5, in some embodiments, be 1.3 to 3.5, or in another other embodiment, be 3.0 to 3.5.In certain embodiments, the pH of colloidal sol or slurry is substantially the same with the pH of the hydrophilic material that provides in step of the present invention (a).In some embodiment of method of the present invention, this colloidal sol or slurry are by at first providing its pH this type of colloidal sol or slurry greater than required pH, then acid is added in this colloidal sol or the slurry and be no more than 3.5 until the pH of colloidal sol or slurry, or be 1.3-3.5 in some embodiments, or till in another other embodiment, being 3.0-3.5 and final the acquisition.For example; as previously mentioned; the photocatalyst material that is used for composition of the present invention can comprise the colloidal sol of the titanium dioxide that is purchased with trade(brand)name NTB-1 and/or NTB-13 from Showa Denko Corporation, and wherein this colloidal sol comprises brookite type titanium dioxide particle or brookite type and Detitanium-ore-type and/or the rutile titanium dioxide particulate mixture that is dispersed in the water.NTB-1 and NTB-13 are typically provided with 2 to 4 pH by supplier.

Acid with the pH that regulates it be can add in the colloidal sol that comprises this photocatalyst material or the slurry to and as previously described mineral acid and organic acid comprised.In certain embodiments of the invention, add to the colloidal sol that comprises photocatalyst material or the acid in the slurry be with the hydrophilic material that adds in step of the present invention (a) in same acids.

Method of the present invention comprises that the hydrophilic material that will provide mixes with colloidal sol that provides or slurry so that photocatalyst material is dispersed in step in the hydrophilic material in step (b) in step (a).This mixing step is not particularly limited and can finishes by any common hybrid technology well known by persons skilled in the art, as long as this mixing obtains the dispersion of photocatalyst material in hydrophilic material.As a result, the invention still further relates to aforesaid liquid composition, wherein the pH of composition is no more than 3, as 1.3 to 3.5, or in some embodiments, 3.0 to 3.5.

According to some other method of the present invention, this liquid composition is prepared as follows: the hydrophilic material of the organosilicon acid esters that comprises basically hydrolysis fully (a) is provided, and wherein the pH of hydrophilic material is 7.0-8.5; (b) provide and comprise colloidal sol or the slurry that is dispersed in the photocatalyst material in the thinner; Wherein the pH of colloidal sol or slurry is 7.0-8.5; (c) hydrophilic material that will provide in (a) mixes so that photocatalyst material is dispersed in the hydrophilic material with colloidal sol that provides in (b) or slurry.

These methods of the present invention comprise the step of the hydrophilic material that the organosilicon acid esters that comprises basically hydrolysis fully is provided, and wherein the pH of hydrophilic material is 7.0-8.5, as 7.0-8.0, or are 7.5-8.0 in some embodiments.In some embodiment of these methods of the present invention, this hydrophilic material is by at first providing the material of the organosilicon acid esters that comprises basically hydrolysis fully, wherein the pH of this material is lower than required pH, then alkali cpd being added in this material until the pH of this material is 7.0-8.5, as 7.0-8.0 or be till the 7.5-8.0 in some cases and final the acquisition.

In some embodiment of these methods of the present invention, before the interpolation of as previously described alkali cpd, hydrophilic material can dilute with water.

The material of regulating its pH in the hydrophilic material be can add to and organic bases and mineral alkali comprised.The specific examples of alkali that can be used for improving the pH of hydrophilic material comprises, without limits, alkali metal hydroxide, as sodium hydroxide, potassium hydroxide and lithium hydroxide; Ammonium hydroxide; Quaternary ammonium hydroxide is as tetraethyl ammonium hydroxide and hydroxide tetraethoxide ammonium; Amine such as triethylamine and 3-(diethylamino)-propane-1-alcohol; Hydroxide uncle's sulfonium is as trimethylammonium hydroxide sulfonium and triethyl hydroxide sulfonium; Quaternary phosphonium hydroxides _ as tetramethylphosphonihydroxide hydroxide base _ and hydroxide tetraethyl-_; The organosilicon alkoxide, as gamma-amino propyl silane triol tripotassium salt, N-(beta-aminoethyl)-gamma-amino propyl silane triol tripotassium salt, dimethylsilane glycol di-potassium, trimethyl silanol sylvite, the dimethylsilane glycol is two-tetramethyl ammonium, and the dimethylsilane glycol is two-tetraethyl-ammonium salt and trimethyl silanol tetraethyl-ammonium salt; Sodium acetate; Water glass; Bicarbonate of ammonia; With their mixture.

These methods of the present invention comprise providing and comprise the colloidal sol that is dispersed in the photocatalyst material in the thinner or the step of slurry, and wherein the pH of colloidal sol or slurry is 7.0-8.5, as 7.0-8.0 or be 7.5-8.0 in some embodiments.In certain embodiments, the pH of colloidal sol or slurry is substantially the same with the pH of hydrophilic material (a).In some embodiment of these methods of the present invention, this colloidal sol or slurry are lower than this type of colloidal sol or the slurry of required pH by its pH at first is provided, then alkali being added in this colloidal sol or the slurry until the pH of colloidal sol or slurry is 7.0 to 8.5, as 7.0 to 8.0 or be till 7.5 to 8.0 in some embodiments and final the acquisition.

Alkali with the pH that regulates it be can add in the colloidal sol that comprises this photocatalyst material or the slurry to and as previously described mineral alkali and organic bases comprised.In certain embodiments of the invention, add to the colloidal sol that comprises photocatalyst material or the alkali in the slurry be with the hydrophilic material that adds in step of the present invention (a) in identical alkali.

These methods of the present invention comprise further that the hydrophilic material that will provide mixes with colloidal sol that provides or slurry so that photocatalyst material is dispersed in step in the hydrophilic material in step (b) in step (a).This mixing step is not particularly limited and can finishes by any common hybrid technology well known by persons skilled in the art, as long as this mixing obtains the dispersion of photocatalyst material in hydrophilic material.Have been found that by the liquid composition of this method preparation and can stablize 24-72 hour that a spot of precipitation is only arranged.As a result, the invention still further relates to aforesaid liquid composition, wherein the pH of composition is 7.0 to 8.5, as 7.0 to 8.0, or in some cases 7.5 to 8.0.

Referring now to Fig. 2 and 3,, can find respectively (i) some non-limiting embodiments of the present invention magni-scale schematic cross-sectional view and the Photomicrograph of embodiment of the present invention (ii) has been described.From Fig. 2 and 3, find out, in certain embodiments of the invention, formed photocatalyst material wherein and be dispersed in coating in the whole wetting ability base-material.In these embodiments, coating comprises that the photocatalyst material of nano-scale particle size photocatalytic particle 10 forms is (in these specific embodiments, this particle has the average crystal diameter that is no more than 20 nanometers), they are evenly dispersed in the whole wetting ability base-material 20 relatively.Especially, as being clear that among Fig. 3, these particle 10 right and wrong are coalescent, that is, particle is all or almost all sealed by base-material and separated, rather than combines each other.Although be not bound by any theory, it is believed that this photocatalytic particle can be dispersed in the hydrophilic material fully by the pH of control hydrophilic material and photocatalyst material colloidal sol or slurry before their blending, make coalescent the prevention that this has obtained the liquid composition of low turbidity.Therefore, the invention still further relates to liquid composition with low turbidity as described below.

Because prevent that this light-catalysed particle is coalescent in some composition of the present invention, composition can be applied directly on the organic membrane and cause seldom directly contacting between photocatalyst material such as titanium dioxide granule and organic membrane (if any).As a result, an advantage of embodiment of the present invention is liquid compositions directly on the paint organic membrane, and need not that any barrier layer is arranged between composition of the present invention and organic membrane.One skilled in the art will recognize that by the photocatalysis of photocatalyst material such as titanium dioxide produce-the OH free radical will make on the contrary and degrade with the organic membrane that photocatalyst material directly contacts.

Liquid composition of the present invention and/or an advantage of producing the method for liquid composition of the present invention are that they can form stable single packed liq composition.Therefore, the invention still further relates to single packed liq composition.Here the term of Shi Yonging " single packed liq composition " refers to a kind of like this liquid composition, and each component that wherein constitutes this liquid composition is stored in single container together.

Single packed liq combination of the present invention comprises at least two kinds of components, comprises the photocatalyst material and the wetting ability base-material of previous discussion.In addition, single packed liq composition of the present invention has at least 3 months storage life.Time span between when here the turbidity that the term of Shi Yonging " storage life " refers to when each component blending is in single container and precipitation or cohesion have occurred to liquid composition increases the degree that makes composition no longer can form the low haze film.According to certain embodiments of the present invention, stable single packed liq composition has at least 3 months storage life, or in some other embodiment, at least 6 months, or, in other embodiments, at least 12 months storage life.

In certain embodiments, liquid composition of the present invention is at 3 months, 6 months or have the turbidity that is no more than 600 NTU after 12 months, or be no more than 400 NTU (turbidity unit) in some cases in some cases.Here Bao Dao haze values can be by by Shaban Manufacturing Inc, and the turbidometer DRT-100D type that H.F.Instruments Division makes uses sample cuvette with flat 28mm diameter * 91mm length to measure.In addition, in certain embodiments, has low haze by sedimentary the filming of composition of the present invention.Here " low haze " of Shi Yonging refers to that film has and is no more than 0.3% mist degree.Here the haze value of report can enough turbidometers, and as from Pacific ScientificCompany, the Hazegard_Model No.XL-211 that Silver Spring, Md are purchased measures.

Liquid composition of the present invention also can exist with the form of many wrapped products.Therefore, the invention still further relates to many wrapped products, it comprises first component of the photocatalyst material that comprises previous discussion and comprises second component of the wetting ability base-material of previous discussion.Here the term of Shi Yonging " many wrapped products " refers to comprise the coating products more than a kind of component, wherein each component blending before being about to be applied on the base material.

The invention still further relates to method with the liquid composition coated substrate.These methods of the present invention may further comprise the steps: (a) apply liquid composition and (b) solidify said composition on base material.Base material can clean with for example alcohol/water mixture, and in the preceding drying of carrying out of step (a).The liquid composition that is used for these methods of the present invention comprises the photocatalyst material and the wetting ability base-material of previous discussion.

In these methods of the present invention, liquid composition can be applied on the base material by any required technology, for example spraying, and roller coat, dip-coating, spin coating, flow coat is brushed, and wiping.Liquid composition of the present invention can be applied over polymkeric substance, pottery, concrete, cement, glass, timber, paper or metal base, their matrix material, or on other material, comprise the painted base material.As suggested in the front, liquid composition of the present invention can be effectively on the organic membrane that directly paint exists on may the surface of this base material.If necessary, can apply a plurality of layers of composition of the present invention.Can " anchoring " composition of the present invention with the base material of silanol group reaction, therefore improved binding property is provided.

The specific examples that can apply the goods of liquid composition of the present invention thereon comprises, without limits, and window; At automobile, aircraft, the windshield glass on the ship etc.; Indoor and outdoor reflective mirror; Lens, glasses or other opticinstrument; The sports goggles of protectiveness; Mask; Helmet shield; The glass slide plate of frozen product display con-tainer; Lens; The buildings wall; The buildings roof; Outside ceramic tile on buildings; Structural stone; The painted steel plate; Aluminium sheet; Sash; Screen door; Fence gate; Solarium; Handrail; The greenhouse; Road sign; Transparent sound barrier; Signboard; Billboard; Guardrail; The reflective thing of road; Ornamental panelling; Solar cell; Painted surface on automobile, ship, aircraft etc.; Painted surface on lamp, fixture and other goods; Air conditioning system and cleaner; Kitchen and bathroom internal equipment and equipment; Ceramic tile; Air filter; The store display cabinet; Graphoscope; Heat exchanger of air condition; High-tension cable; The interior external member of buildings; Window glass; Tableware; The wall of living space, bathroom, kitchen, hospital room, factory floor space, office space or the like; Sanitary apparatus is as washbowl, bathtub, w.c.pan, urinal, rinse bath or the like; And electronics, as graphoscope.

Liquid composition of the present invention can be by for example being applied on the base material with liquid composition impregnate paper of the present invention, cloth or nonwoven fabric.The material of dipping can be stored in container, takes out the wiping coated substrate surface when needs.Additionally, paper, cloth or nonwoven fabric can be in use with liquid composition dippings of the present invention.

In the method for coated substrate of the present invention, liquid composition is cured after on being applied over base material, and is promptly dry.Though be not bound by any theory, it is believed that after solidifying some silanol group generation condensations of the base-material of hydrolysis fully basically make to have formed the Si-O-Ti key in the dry film that forms from liquid composition.The existence that it is believed that these groups has strengthened from the weather resistance of the coating of composition formation of the present invention, and this will be described in greater detail below.

Liquid composition can be a self cure, makes composition to be cured under the help without any curing catalysts.In addition, liquid composition of the present invention can for example solidify at ambient temperature.In other words, the curing of liquid composition of the present invention can be placed in air by said composition, and promptly dry air is finished.According to certain embodiments of the present invention, this liquid composition is to solidify by following manner: allow it be exposed to air under 25 ℃ and reach 2-3 hour and obtain Superhydrophilic and be exposed to air and reach 16 hours and obtain long durability.Liquid composition of the present invention also can solidify by heat drying.For example, according to certain embodiments of the present invention, liquid composition can reach 3-5 minute and force its drying to be cured at least 3 seconds under 80 ℃ to 100 ℃ then by allowing it be exposed to air.

One in the feature of certain embodiments of the present invention is that liquid composition can have extremely low solids content, and about 1wt% total solids is based on the gross weight of composition.Therefore, this liquid composition can be with on the extremely little film thickness paint base material.Especially, according to certain embodiments of the present invention, composition is that the form with film is applied on the base material, make this film have and be no more than 200 nanometers (0.2 micron), or 10 to 100 nanometers (0.01 to 0.1 micron) in some embodiments, the build of 20 to 60 nanometers in another other embodiment of the present invention (0.02 to 0.06 micron).The coating of composition of the present invention under this low film thickness can particularly advantageously provide optical thin film, and the refractive index of refractive index that will coating and base material mates.

As previously described, the coating that forms from liquid composition of the present invention is hydrophilic at first, that is, after applying and before the exciting of photocatalyst, coating demonstrates the affinity to water.This initial wetting ability obtains and can be being no more than 20 ° or in some embodiments being no more than 15 ° from the wetting ability of base-material, or, in another other embodiment, represent with the initial water contact angle that is no more than 10 °.Yet, by exciting of photocatalyst material, can give " Superhydrophilic " by the coating that liquid composition of the present invention forms, that is, after the exciting of photocatalyst, this coating can demonstrate and be lower than 5 °, even little water contact angle to 0 °.

The mode that can be used for the exciting light catalyzer depends on the photocatalyst material that uses in liquid composition of the present invention.For example, the light activated material by being exposed to visible light, as the brookite form of titanium dioxide, and nitrogen or the adulterated titanium dioxide of carbon, can be exposed to any visible light source, comprise any radiation of at least 400 nano wave lengths.On the other hand, the anatase octahedrite of titanium dioxide and rutile form, stannic oxide and zinc oxide can be by being lower than 387 nanometers respectively, 413 nanometers, the exposure ultraviolet radiation of the wavelength of 344 nanometers and 387 nanometers is carried out optical excitation.The suitable ultraviolet radiation source that is used for this type of photocatalyst of optical excitation comprises, without limits, the UV lamp, as with trade name UVA-340 by Q-Panel Company of Cleveland, those that Ohio sells, it has the intensity of 28 watts/every square metre (W/M2) on coatingsurface.

In certain embodiments, the coating by liquid composition preparation of the present invention demonstrates 0.5cm at least ^-1Min ^-1, as, 1.0cm at least ^-1Min ^-1Photolytic activity.Photolytic activity can be according in U.S. Patent No. 6,027,766, the 11 hurdles, and the 1st walks to the 12nd hurdle, and method is estimated described in the 55th row, and it is hereby incorporated by reference.

In certain embodiments, the coating that is formed by liquid composition of the present invention can reach and became Superhydrophilic in 1-2 hour by being exposed to sunlight.Additionally, the coating that is formed by liquid composition of the present invention can be by being exposed to 28W/m ²The ultraviolet radiation of intensity became Superhydrophilic in 1 hour.

As mentioned above, the coating that is formed by liquid composition of the present invention especially can demonstrate very favorable wetting ability, antistatic property and/or antibacterium performance.Because they are hydrophilic and become Superhydrophilic after the photoexcitations of photocatalyst material, so demonstrate the ideal self-cleaning property from the coating of preparation of compositions of the present invention, didirtresistance, and/or anti-fogging performance.Therefore, the invention still further relates to and make substrate surface have self-cleaning property, antifouling property, and/or the method for anti-fogging performance.

From another feature of the coating of preparation of compositions of the present invention is that they can be competent especially.Can pass the ability of keeping contact angle in time under the weathering condition that quickens according to the film surface from the surprising weather resistance of the coating of preparation of compositions of the present invention measures.In time can be few more after passing or several wiping cycles by the contact angle that institute's test sample is kept, film is durable more.The simulation weathering of film can obtain via the weathering chamber, and it comprises Cleveland condensation cabinet (CCC) and QUV tester (Q-Panel Company, Cleveland, the product of Ohio).

In certain embodiments, this photocatalyst material be enough to be exposed to the CCC chamber form after reaching 4000 hours can keep be lower than 10 degree, as the contact angles that are lower than 5 degree and/or keep 3cm ^-1Min ^-1The consumption of photoactive coating be present in the liquid composition of the present invention, wherein CCC chamber operation under the vapour temperature of 140_ (60 ℃) in indoor environment causes the constant water condensation on testing surface.In fact, illustrated as the embodiment here, Comparatively speaking the composition of having found with the wetting ability base-material that contains here that type of describing but not had a photocatalyst material comprises photocatalyst material and can obtain demonstrating the coating of improved weather resistance significantly in some embodiment of composition of the present invention.Illustrated as Fig. 4, in certain embodiments of the invention, this photocatalyst material can be a kind of even at the initial water contact angle that allows coating be exposed to as mentioned above like that to keep it after reaching 4000 hours in the CCC chamber (promptly to be enough to form, this water contact angle and initial water contact angle differ within 4 degree, wherein " initial water contact angle " refer to be exposed to according to described method in an embodiment UV light reach 2 hours after but viewed water contact angle before being exposed to the CCC chamber) the amount of coating be included in the composition, and do not exist photocatalyst material to obtain after this exposure of approximately 2000-3000 hour, can not keeping the coating of its initial water contact angle.In fact, this embodiment explanation exposes surperficial contact angle after 3500 hours and brings up to almost 3 times of initial contact angle in CCC under the situation that does not have photocatalyst material.Do not wish to be bound by any theory, the contriver believes that this surprising result can form the Si-O-Ti key owing to the partial cross-linked of photocatalyst material and organosilicon acid esters in coating.The contriver believes, some photocatalyst materials have participated in that this is crosslinked, and some photocatalyst materials in addition after CCC exposes 4000 hours still maintenance can be used for light-catalysed activity.

In certain embodiments, can be from the coating of preparation of compositions of the present invention at the contact angle that exposed 650 hours under 65-70 ℃ the blackboard temperature and condensation humidity is kept the 5-6 degree after 4 hours under 50 ℃ of atmosphere temperatures the QUV tester that fluorescent tube bulb (B313 nanometer) is housed.

The following example illustrates the present invention, yet they should not be considered to limit the invention to their detailed content.Except as otherwise noted, whole parts among the embodiment and in whole specification sheets and percentage be by weight below.

Embodiment

Embodiment 1: the preparation of hydrolysis organic silicic acid eater base stocks

The acid hydrolysis catalyst solution, here note is made solution " A ", adds in pure, dry 2 gallon container by the deionized water with 7,000 grams to prepare.Under agitation, add 70% nitric acid of 1.0 grams and leaving standstill.

98%TMOS (the tetramethoxy-silicane) (SiO of representative～6 grams with 15.5 grams (～0.10 mole) ₂) add in purified, dry 1 liter of glass beaker.

The solution A (～0.20 mole H20) of 3.6 grams is added among the TMOS at leisure, control heat release by using the ice bath holding temperature to be lower than 25 ℃.After the interpolation of solution A finishes, this partly the solution of silane of hydrolysis kept 1 hour down at-25 ℃.In independent pure, dry beaker, the ethanol of 290.5 grams and the deionized water of 290.5 grams are mixed, after 1 hour hold-time, when stirring, add in the partial hydrolysate then.Then, under agitation the pH (pH～5) of rare solution of silane is adjusted to pH～3.9 by adding 0.80 gram Glacial acetic acid.Formed 1%SiO ₂The under agitation abundant hydrolysis of base-material solution is spent the night.

Shown good wettability when on test board, applying, do not had the optics flaw, and passed through to keep simultaneously for 50 flushing/drying cycles good hydrophilicity with above solution.

Embodiment 2: the preparation of hydrolysis organic silicic acid eater base stocks

The 98%TMOS (SiO of representative～6 grams with 15.5 grams (～0.10 mole) ₂) and the anhydrous methanols (solubility promoter) of 3.6 grams add in purified, dry 1 liter of glass beaker.The solution A (～0.20 mole H20) of 3.6 grams is added in the TMOS solution at leisure, by the interpolation rate-controlling heat release of solution A.The peak temperature that reaches in the interpolation process is 33 ℃.After the interpolation of solution A finishes, this partly the solution of silane of hydrolysis kept 1 hour down at～25 ℃.In independent pure, dry beaker, the ethanol of 287 grams and the deionized water of 290.5 grams are mixed, after 1 hour hold-time, when stirring, add in the partial hydrolysate then.Then, under agitation the pH (pH～5) of rare solution of silane is adjusted to pH～3.9 by adding 0.80 gram Glacial acetic acid.Formed 1%SiO ₂The under agitation abundant hydrolysis of base-material solution is spent the night.

Apply on test board with above solution and to demonstrate the dewetting problem, and spottiness.Test-results shows, thereby comprising of solubility promoter guaranteed that more effective hydrolysis and corresponding condensation form more high-molecular weight oligopolymer, and this has illustrated viewed behavior when applying.

Embodiment 3: the preparation of hydrolysis organic silicic acid eater base stocks

98%TMOS (the tetramethoxy-silicane) (SiO of representative～6 grams with 15.5 grams (～0.10 mole) ₂) add in purified, dry 1 liter of glass beaker.The solution A (～0.20 mole H20) of 3.6 grams is added among the TMOS at leisure, by the interpolation rate-controlling heat release of solution A.The peak temperature that reaches in the interpolation process is 40 ℃.After the interpolation of solution A finishes, this partly the solution of silane of hydrolysis kept 1 hour down at～25 ℃.In independent pure, dry beaker, the ethanol of 290.5 grams and the deionized water of 290.5 grams are mixed, after 1 hour hold-time, when stirring, be added in the partial hydrolysate then.Then, under agitation the pH (pH～5) of rare solution of silane is adjusted to pH～3.9 by adding 0.80 gram Glacial acetic acid.1%SiO ₂The under agitation abundant hydrolysis of base-material solution is spent the night.

Apply on test board with above solution and to demonstrate the dewetting problem, and spottiness.Test-results shows, by do not control thermal discharge and allow hydrolysis temperature reach～40 ℃, will cause the much higher condensation of degree and form more high-molecular weight oligopolymer, this has illustrated viewed behavior when applying.

Embodiment 4: the preparation of hydrolysis organic silicic acid eater base stocks

(w: w) ratio under agitation mixed by 1: 1 for methyl alcohol and deionized water.Mixture is cooled to room temperature.(Mitsubishi ChemicalCorporation, Tokyo Japan) add in the glass reactor, and the premixed methanol solvent mixture with 504.8g adds as a part subsequently with the MS-51 silicon ester solution of 10.0g.Solution stirred 15 minutes down at 20-22 ℃.Then, under agitation the Glacial acetic acid of 5.2g is added in this reactor.Solution mixture kept stirring other 24 hours at ambient temperature.The final SiO of solution ₂Content is 1%, has 3.5 pH.

Embodiment 5: the preparation of hydrolysis organic silicic acid eater base stocks

(w: w) ratio under agitation mixed by 1: 1 for 1-propyl alcohol and deionized water.Mixture is cooled to room temperature.In independent container, the Glacial acetic acid that dilutes 10.0g by the 1-propanol/water solvent mixture with 90.0g prepares acetic acid solution.The MS-51 silicon ester solution of 5.0g is added in the glass reactor, and the premixed 1-propanol/water solvent mixture with 253.7g adds as a part subsequently.Solution stirred 15 minutes down at 20-22 ℃.Then, under agitation the prefabricated acetic acid solution of 1.4g is added in this reactor.Solution mixture kept stirring other 24 hours at ambient temperature.The final SiO of solution ₂Content is 1%, has 4.1 pH.

The preparation of embodiment 6-liquid composition

Liquid composition A-G in table 1 is prepared as follows.In being housed, 1 liter of Glass Containers of magnetic stirring bar prepares the I that feeds intake.By base material being added in this container, under agitation deionized water being added in this container then and prepare the I that feeds intake.By under agitation adding 2N hydrochloric acid till reaching required pH, with the pH regulator to 1.8 of mixture.

In being housed, 4 oz glass containers of magnetic stirring bar prepare the II that feeds intake.TiO 2 sol is added in this container, then by under agitation adding 2N hydrochloric acid till reaching required pH, pH regulator to 1.8.The II that feeds intake under agitation is added among the I that feeds intake then, produces hydrophilic compositions A-G.

Table 1

Composition	Silicon ester/TiO 2Weight ratio	Base-material 1	Deionized water	TiO 2 sol 2	TiO 2 sol 3
						A	0.5/0.3	500g	480g	20g	--
B	0.5/0.3	500g	480g	20g	--
						C	0.4/0.24	40g	58.4g	1.6g	--
D	0.31/0.19	31g	67.7g	1.27g	--
						E	0.25/0.25	25g	73.3g	1.67g	--
F	0.9/0.1	47g	2.3g	0.33g	--
						G	0.5/0.3	25g	24.5g	--	0.5g

¹From Mitsubishi Chemical Corporation, the MSH-200 hydrolysis organosilicon acid esters (1% solid) that Tokyo, Japan are purchased.

²From Showa Denko K.K., the NTB-1 TiO 2 sol that Tokyo, Japan are purchased.

³The STS-01 TiO 2 sol that is purchased from Ishihara Sangyo Kaisha Ltd.

Embodiment 7-float glass test substrate

Employing by dilute dense Dart 210 with deionized water so that solution has prepared rare Dart 210 solution of the concentration of 5%-10%Dart210 (from Madison Chemical Co., Inc. be purchased) clean base material, prepare 9 " * 12 " surface of float glass test substrate.Base material is used the hot tap water rinsing then, uses rinsed with deionized water then.Test substrate is sprayed with Windex_, and dries with paper handkerchief (Kaydry_ that is purchased from Kimberly-Clark Corp.).

The liquid composition of embodiment 6 by using the BLOODBLOC Protective Pad that is purchased from Fisher Scientific, is applied on the test substrate by the wiping cladding process separately.With this this foam applicator of pad parcel.Then, by using dropper or having the Plastic Bottle of liquid droping head that 1.5 hydrophilic compositions that restrain are applied on this pad.Composition then by allowing wet pad contact with the glass test substrate with straight, a little eclipsed road (strokes) apply.After coating, before test, allow base material drying at least 2 at room temperature.The result is summarised in the table 2.

Table 2

Composition	Ti (μg/cm 2) 1	PCA (cm -1min -1) 2	Surface resistivity (ohms/cm 2) 3	Mist degree 4
					A	1.2	3.9	3.84×10 9	0.1％
B	2.3	8.1	6.25×10 8	0.2％
					C	0.7	2.1	--	--
D	0.5	1.3	--	--
					E	0.7	2.6	--	--
F	0.4	0.6	--	--
					G	1.9	5.5	--	--

¹The sample that uses X-ray fluorescence method to analyze.

²Photocatalytic activity is according in U.S. Patent No. 6,027,766, the 11 hurdles, and the 1st walks to the 12nd hurdle, and method is estimated described in the 55th row.

³Surface resistivity ACL Statitide Model 800 Megohmeter, by using (1) big elongated probe of 5 millimeters placements at interval on the several position on the sample, or (2) on the several position on the sample at interval the probe on the plate of this instrument of 2.75 inches estimate.

⁴Haze value Company from Pacific Scientific, the Hazegard_Model No.XL-211 haze meter that Silver Spring, Md are purchased is estimated.

Endurance test-test 1

The test substrate that scribbles liquid composition A and B is placed in the Cleveland condensing chamber of operation under the 140_ (60 ℃).Each test substrate per week is taken out from this chamber and tests to measure water contact angle.By measuring before base material is exposed to UV light and water contact angle difference is afterwards measured the photolytic activity of composition.Exposure interval is for being exposed to the ofCleveland by Q-Panel Company, the UVA-340 lamp of Ohio supply or 2 hours of direct sunlight.The water contact angle of being reported is by using by Lord Manufacturing, and the bubble telltale is caught in Inc. improvement that make, that Gartner Scientific protractor optical element is housed, measures by stopping the method for dripping.The surface that will measure is placed on level attitude, towards last, in the front of light source.The water that will stop to drip is placed on the top on surface of light source front, and contact angle (pressing the number of degrees) be observed and be measured to the profile that stops like this to drip can by the graduated protractor farsighted glasses of circular protractor is housed.The result is summarised in the table 3.

Table 3

	Composition A		Composition B
					Hours in CCC	Contact angle before the exposure	Contact angle after the exposure	Contact angle before the exposure	Contact angle after the exposure
0	20	3	12	3
					498	14	3	12	3
1062	38	3	37	3
					1535	32	3	27	3
2221	18	4	9	3
					2573	30	3	26	3
2975	30	5	33	4
					3565	--	--	30	5
4040	--	--	19	4

Endurance test-test 2

The weather resistance of test substrate that scribbles liquid composition A-G is tested but measured water contact angle before in putting into the Cleveland condensing chamber by after the aforesaid UV of being exposed to light.Then identical base material is put among the aforesaid CCC and reached at least 4000 hours, taking-up then.Base material is exposed to aforesaid UV light then and tests by measuring water contact angle.The result is summarised in the table 4.

Table 4

Composition	Contact angle before the CCC exposure	Contact angle after 4000 hours CCC
			A	3	5
B	3	4
			C	5	4
D	5	3
			E	6	2
F	5	9
			G	3	3

Endurance test-test 3

Scribble composition of the present invention test substrate weather resistance also with scribble the base material that comprises hydrophilic organic silicon acid esters base-material but do not contain the composition of photocatalyst material and compare.With hydrophilic compositions B and the F of embodiment 6 and have the base-material of 0.95/0.5 and the analogous composition of titanium dioxide ratio (composition J) is put in the aforesaid Cleveland condensing chamber (CCC), periodically take out as mentioned above and be exposed to UV light.Comparative composition A is from DainipponShikizai, and the Shinsui Flow MS-1200 that Tokyo, Japan are purchased, Comparative composition B are from Mitsubishi Chemical Corporation, the MSH-200 that Tokyo, Japan are purchased.Test substrate is tested aforesaid water contact angle.The results are shown among Fig. 4.

The preparation of embodiment 8-liquid composition

Prepare liquid composition H and I according to the mode of describing in embodiment 1, different is that WINDEX is included in the composition and base-material/TiO with the amount of indicating in the table 5 ₂Weight ratio is according to regulating shown in the table 5.The weather resistance of these compositions is analyzed according to the mode of describing in endurance test-test 1 then.The results are shown in Table 6.

Table 5

Composition	Silicon ester/TiO 2Weight ratio	Base-material/TiO 2Amount 1	The amount of WINDEX
				H	0.35/0.25	30g	8.91g
I	0.35/0.25	30g	6.26g

Table 6

	Composition H		Composition I
					Hours in CCC	Contact angle before exposure	Contact angle after exposure	Contact angle before exposure	Contact angle after exposure
0	4	4	5	4
					330	27	2	21	2
834	19	2	31	2
					2390	26	3	23	5
3374	18	3	16	3
					4022	38	4	32	11

The turbidity of embodiment 9-liquid composition

Prepare liquid composition K, L, M and O according to the mode of describing in embodiment 6, different is to the value of listing in table 7 and base-material/TiO with pH regulator ₂Weight ratio is according to regulating shown in the table 7.Prepare liquid composition N, P and Q according to the mode that is similar to embodiment 6, different is, and the feed intake pH of I does not regulate, the II that feeds intake is the mixture of TiO 2 sol and deionized water, and wherein the amount of deionized water is enough to deionized water TiO 2 sol is diluted to 2% solid from 15% solid.The pH of II of feeding intake does not regulate, and the II that feeds intake added to prepares this liquid composition among the I that feeds intake.The haze values of these compositions is passed through then by ShabanManufacturing Inc, the turbidometer DRT-100D type that H.F.Instruments Division makes uses the sample cuvette with flat 28mm diameter * 91mm length As time goes on to analyze.The results are shown in Table 7.

Table 7

			Turbidity (NTU)
							Composition	Silicon ester/TiO 2Weight ratio	pH	Initially	1 month	3 months	6 months
K	0.5/0.3	1.96	490	558	569	652
							L	0.5/0.3	1.57	438	552	567	653
M	0.35/0.2	1.8	321	383	393	442
							N	0.35/0.2	3.25	454	412	385	425
O	0.4/0.25	1.8	415	488	511	573
							P	0.5/0.1	3.1	145	143	145	153
Q	0.9/0.1	3.11	149	143	145	162

The fog resistance of embodiment 10-on plastic lens

Present embodiment is used to illustrate anti-fogging performance of the present invention.The thermoplastic poly carbonic ether lens that applied not painted hard coat (Gentex_PDQ_, from Gentex Optics, Inc is purchased) by supplier are by with soap and water washing, carry out surface treatment with deionized water and isopropyl alcohol and dry air in advance.These lens carry out Cement Composite Treated by Plasma then.For embodiment 10A, there is not additional coatings to be applied on the lens.For embodiment 10B, the lens of plasma surface treatment Corporation from Mitsubishi Chemical, the MSH-200 hydrolysis organosilicon acid esters (1% solid) that Tokyo, Japan are purchased applies.For embodiment 10C, the lens of plasma surface treatment are coated in the composition of the type of describing among the embodiment 6, composition E by the dip coating method with the extraction yield (extraction rate) of 230mm/min.

Knot mist performance is estimated by lens being placed on the cup that hot water is housed.The lens of embodiment 10A are at its entire area upper fogging.The lens of embodiment 10B are at the 50-60% of its area upper fogging.The lens of embodiment 10C are not tied mist in its surface.

The resistance to crocking of the embodiment 11-dust of anti-the braking automobile

Present embodiment is used to illustrate antifouling property of the present invention.Use masking tape to be divided into five homogeneous areas from two aluminum-alloy wheels that DaimlerChrysler buys.These wheels are installed on the 1996 type Ke Lesile Jeep Cherokee cars, and one of them wheel (wheel #1) is installed in the front passenger side, and another wheel (wheel #2) is installed in the front driver side.Before installing, five zones of each are performed as follows processing among wheel #1 and the wheel #2.

Wheel #1 preparation

Before being installed on the vehicle, five zones of wheel #1 are performed as follows processing.Coating is not coated on the zone 1.Use washing bottle to apply Hi-Gard regional 2 by the curtain coating method ^TM1080 (from PPG Industries, the coating solution that contains organosilane that Inc. is purchased), dry air 5 minutes and in down baking 3 hours of 240_ (116 ℃).With above described the same for regional #2, zone 3 is coated with Hi-Gard1080.After baking, zone 3 is then by applying from Mitsubishi ChemicalCorporation the MSH-200 hydrolysis organosilicon acid esters (1% solid) that Tokyo, Japan are purchased with soaking sponge with the wiping cladding process.MSH-200 is dry air and from condensation then.With above described the same for zone 2, zone 4 is coated with Hi-Gard1080.After toasting, the composition of sponge with type described in the wiping cladding process coating embodiment 6, the i.e. mixture of composition E and deionized water and ethanol (50/50 weight ratio) are soaked by using in zone 4.The composition of type described in the 5 usefulness embodiment 6 of zone, promptly composition E applies.

One week of vehicle drive.Before water rinse, the regional 1-5 of wheel #1 does not demonstrate significant difference on degree of cleaning.After using from the gardening usefulness water rinse of flexible pipe, the degree of cleaning of the regional 1-5 of wheel #1 are measured according to the scale of 1-10, and higher numerical value reflection records than clean Surface.The results are shown in the table 8.

Table 8

The zone	Degree of cleaning
		1	2
2	6
		3	8
4	10
		5	10

Wheel #2 preparation

Before being installed on the vehicle, five zones of wheel #2 are performed as follows processing.Coating is not coated on the zone 1.Use washing bottle 2 to apply SolGard_330 coating (from PPG Industries, the coating solution that contains organosilane that Inc. is purchased) in the zone, dry air 5 minutes and in 240_ (116 ℃) baking 3 hours down by the curtain coating method.With above described the same for zone 2, zone 3 is coated with Hi-Gard1080.After baking, zone 3 is then by applying from MitsubishiChemical Corporation the MSH-200 hydrolysis organosilicon acid esters (1% solid) that Tokyo, Japan are purchased with soaking sponge with the wiping cladding process.MSH-200 is dry air and from condensation then.With above described the same for zone 2, zone 4 is coated with Hi-Gard1080.After toasting, the composition of sponge with type described in the wiping cladding process coating embodiment 6, the i.e. mixture of composition E and deionized water and ethanol (50/50 weight ratio) are soaked by using in zone 4.The composition of type described in the 5 usefulness embodiment 6 of zone, promptly composition E applies.

One week of vehicle drive.Before water rinse, the regional 1-5 of wheel #1 does not demonstrate significant difference on degree of cleaning.After using from the gardening usefulness water rinse of flexible pipe, the degree of cleaning of the regional 1-5 of wheel #1 are measured according to the scale of 1-10, and higher numerical value reflection records than clean Surface.The results are shown in the table 9.

Table 9

The zone	Degree of cleaning
		1	2
2	8
		3	10
4	10
		5	10

Embodiment 12A and 12B-are applied on the painted surface

Embodiment 12A: add in the liquid composition (being composition E) of 100 those types described among embodiment 6 that restrain by the Surfynol465 (can obtain from Air Products) with three grams, stirring the mixture then prepares liquid composition.

The plate preparation

Pass through to use the coiling drawdown rod with the pretreated aluminium sheet of Betz Permatreat1500, (can be from PPG Industries, Inc. obtains) applies with 0.7-0.8 mil build with the white polyester coating of Truform_ZT high gloss.The aluminium sheet that applies toasted 30 seconds down at 450_ (peak value metal temperature).For embodiment 12 (1), do not increase additional coating.For embodiment 12 (2), more than prepared hydrophilic compositions by using the coiling drawdown rod, be applied on the aluminium sheet that Truform ZT-painted with 0.05-0.15 mil build.This plate toasted 25 seconds down at 350_ (peak value metal temperature).

The exposure test result

Coated board and uncoated plate compare after Malaysia places 6 months.The results are shown in Table 10.

Table 10

	The placement of 6 months plates of Malaysia: level		The position of 3 months plates in Florida State, south: 45 ° towards south
					Embodiment	Do not wash Δ L 1	Washing Δ L	Do not wash Δ L	Washing Δ L
12(1)	-21.6	-13.82	-6.05	-4.02
					12(2)	-8.30	-1.00	-3.35	-0.01

¹By using the MacBeth Color Eye_2145 spectrophotometric determination luminance brightness (L) that obtains from Macbeth division of Kollmorgen Instruments.Luminance brightness is measured before exposing and is carried out afterwards and write down difference (dL).DL value representation preferable performance near zero (plus or minus).The look that low Δ L value representation is lower becomes.Negative value refers to compare with the initial color reading, and coating becomes darker color.Low Δ display plate in not washing the zone is not too dirty under the situation that does not have washing.

Embodiment 12B: used the pretreated aluminium sheet of Betz Permatreat1500 according to applying with Duranar_ semi-gloss coating (can be from PPGIndustries, Inc. obtains) with the similar approach described in the embodiment 12A.

For embodiment 12 (3), by using the coiling drawdown rod, be applied on the aluminium sheet that Duranar painted with 0.05-0.15 mil build at the liquid composition described in the embodiment 12A.This plate toasted 25 seconds down at 350_ (peak value metal temperature).For embodiment 12 (4), Toto Frontier Research Co., Ltd. covers with paint, lacquer, colour wash, etc. this lacquered board with the low varnish of safeguarding that contains titanium dioxide.Embodiment 12 (3) and 12 (4) plate expose 13 months and 14 months in southern Florida State.On the plate of embodiment 12 (4), observe cracking, on the plate of embodiment 12 (4), do not observe cracking.

Embodiment 13: be applied on the millwork base material

Specimen preparation: control sample is Laboratory Production or the industrial plate with commodity solvent borne polyurethane millwork paint finishing.By at first preparing test portion with the isopropyl alcohol some parts.Then, by on these parts lightly the paper cloth that soaked of wiping be coated in the liquid composition of type described in the embodiment 6, i.e. composition E.One night of coating dry air.On four kinds of base materials, prepare sample; The door base material (FWD) that paper phenol coats, glass fibre pultrusion (pult), glass fibre pultrusion (VCP) and pine window substrate (NLP) that Vinylite coats.Sample is sent in Malay exposed location and carries out exposing in 3 months, is sent and estimate back to variable color and gloss retention then.The results are shown in Table 11.

Table 11

Base material	NLP		FWD		Pult.		VCP
									Sample	Contrast	Embodiment 7A	Contrast	Embodiment 7B	Contrast	Embodiment 7C	Contrast	Embodiment 7D
Colour-change	14.3	8.9	12.7	4.7	16.4	2.7	10.8	2.3
									% gloss retention rate	54	47	76	108	69	87	71	71

It will be readily appreciated by those skilled in the art that and do not breaking away under the prerequisite of the disclosed design of aforementioned specification and can improve the present invention.This type of improvement will be believed to comprise within claims, unless claim is according to the other explicit state of their wording.Therefore, embodiment described in detail here only is to illustrate not limit the scope of the invention, whole width that scope of the present invention is provided by claims and all equivalency range thereof.

Claims (33)

1. liquid composition comprises:

(a) photocatalyst material and

(b) comprise basically the wetting ability base-material of the organosilicon acid esters of hydrolysis fully.

2. the liquid composition of claim 1, wherein at least a portion of photocatalyst material exists with the particle form of average crystal diameter with 3-35 nanometer.

3. the liquid composition of claim 1, wherein this photocatalyst material is selected from the titanium dioxide of brookite form, is carried out the adulterated titanium dioxide of titanium dioxide, nitrogen, Cement Composite Treated by Plasma titanium dioxide and their mixture of chemical modification by flame pyrolysis.

4. the liquid composition of claim 1, wherein this photocatalyst material provides with the particulate solation that comprises the photocatalyst material that is dispersed in the water.

5. the liquid composition of claim 1, wherein this photocatalyst material is present in the liquid composition with the amount of 0.1-0.75wt%, based on the gross weight of composition.

6. the liquid composition of claim 1, wherein the organosilicon acid esters is selected from organic radical TMOS, organic radical oxygen radical siloxane and their mixture, and wherein this organic radical TMOS is selected from tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, tetraisobutoxy-silicane alkane, four sec-butoxy silane, four tert.-butoxy silane, tetraphenoxy-silicane alkane, dimethoxy diethoxy silane and their mixture.

7. the liquid composition of claim 1, wherein the organosilicon acid esters is to press SiO ₂The amount of meter 0.1-2wt% is present in the liquid composition, based on the gross weight of composition.

8. the liquid composition of claim 1, wherein photocatalyst material and organosilicon acid esters are present in the liquid composition with 0.05: 0.95 to 5: 0.3 ratio by weight.

9. the liquid composition of claim 1, wherein the pH of composition is no more than 3.5.

10. the liquid composition of claim 1, wherein the pH of composition is 7.0-8.5.

11. scribble the base material of the cured film that the liquid composition by claim 1 forms.

12. the base material of claim 11, wherein film has the build of 20 to 60 nanometers.

13. the base material of claim 11, wherein before the photoexcitation of photocatalyst material, film demonstrates the initial water contact angle that is no more than 10 °.

14. the base material of claim 11, wherein, after the exciting of photocatalyst, film demonstrates and is lower than 5 ° water contact angle.

15. make the method for the liquid composition of claim 1, this method may further comprise the steps:

(a) provide the hydrophilic material of the organosilicon acid esters that comprises basically hydrolysis fully, wherein the pH of hydrophilic material is no more than 3.5;

(b) provide and comprise colloidal sol or the slurry that is dispersed in the photocatalyst material in the thinner, wherein the pH of colloidal sol or slurry is no more than 3.5; With

(c) hydrophilic material that will provide in step (a) mixes so that photocatalyst material is dispersed in the hydrophilic material with colloidal sol that provides in step (b) or slurry.

16. the method for claim 15, wherein the hydrophilic material that provides in step (a) provides the water wetted material of the organosilicon acid esters that comprises basically hydrolysis fully by (1), wherein the pH of water wetted material greater than required pH and (2) add acid in this water wetted material till reaching required pH and final the acquisition.

17. the method for claim 15, wherein colloidal sol that provides in step (b) or slurry provide by (1) and comprise colloidal sol or the slurry that is dispersed in the photocatalyst material in the thinner, wherein the pH of colloidal sol or slurry greater than required pH and (2) add acid in this colloidal sol or the slurry till reaching required pH and final the acquisition.

18. make the method for the liquid composition of claim 1, this method may further comprise the steps:

(a) provide the hydrophilic material of the organosilicon acid esters that comprises basically hydrolysis fully, wherein the pH of hydrophilic material is 7.0-8.5;

(b) provide and comprise colloidal sol or the slurry that is dispersed in the photocatalyst material in the thinner, wherein the pH of colloidal sol or slurry is 7.0-8.5; With

(c) hydrophilic material that will provide in step (a) mixes so that photocatalyst material is dispersed in the hydrophilic material with colloidal sol that provides in step (b) or slurry.

19. the method for claim 18, wherein the hydrophilic material that provides in step (a) provides the water wetted material of the organosilicon acid esters that comprises basically hydrolysis fully by (1), wherein the pH of water wetted material be lower than required pH and (2) add alkali in this water wetted material till reaching required pH and final the acquisition.

20. the method for claim 18, wherein colloidal sol that provides in step (b) or slurry provide by (1) and comprise colloidal sol or the slurry that is dispersed in the photocatalyst material in the thinner, wherein the pH of colloidal sol or slurry be lower than required pH and (2) add alkali in this colloidal sol or the slurry till reaching required pH and final the acquisition.

21. the liquid composition of claim 1, wherein liquid composition is the form of single packed liq composition with storage life of at least 3 months.

22. the composition of claim 21, wherein single packed liq composition has at least 6 months storage life.

23. the composition of claim 22, wherein single packed liq composition has at least 12 months storage life.

24. the composition of claim 23, wherein composition had the turbidity that is no more than 600 NTU after 3 months.

25. the method for coated substrate may further comprise the steps:

(a) on base material, apply claim 1 liquid composition and

(b) curing composition.

26. the method for claim 25, wherein composition reaches at least two hours and solidifies by allowing said composition be exposed to air under 25 ℃.

27. the liquid composition of claim 1, wherein photocatalyst material a kind ofly still keeps the amount of the coating of its initial water contact angle to be present in the liquid composition after reaching 4000 hours being exposed to the Cleveland condensing chamber to be enough to produce, wherein operate in room ambient under the vapor temperature of 140_ (60 ℃) the CCC chamber, causes the constant water condensation on testing surface.

28. the liquid composition of claim 1, wherein photocatalyst material a kind ofly is present in the liquid composition being exposed to the amount of coating that the Cleveland condensing chamber still keeps below the contact angles of 10 degree after reaching 4000 hours to be enough to produce, wherein operate in room ambient under the vapor temperature of 140_ (60 ℃) the CCC chamber, causes the constant water condensation on testing surface.

29. the liquid composition of claim 1, wherein this base-material prepares by being selected from following technology:

(a) multistage process, it comprises: wherein react the fs that forms the partial hydrolysis polycondensation product in the presence of the acid hydrolysis catalyzer by organosilicon acid esters and water, wherein the amount of water is lower than the stoichiometric amount of organic radical oxygen base that can this organosilicon acid esters of hydrolysis, wherein partial hydrolysis polycondensation product contacts with a large amount of water and forms the organosilicon acid esters subordinate phase of hydrolysis fully basically, with

(b) allow tetraalkoxysilane oligopolymer and water in the presence of organic acid hydrolyst and/or organic solvent, react, wherein the amount of water is significantly greater than the stoichiometric amount of organic radical oxygen base that can this organoalkoxysilane of hydrolysis, thereby forms the organosilicon acid esters of hydrolysis fully basically.

30. the liquid composition of claim 29, wherein this base-material prepares by multistage process.

31. the liquid composition of claim 30, wherein water exists with 50% stoichiometric amount of organic radical oxygen base that can hydrolysis organosilicon acid esters in the fs.

32. the liquid composition of claim 30, wherein the fs carries out under the condition of restriction owing to the condensation degree of the formed Si-OH group of hydrolysis reaction.

33. the liquid composition of claim 32, wherein restriction is owing to the condition of the condensation degree of the formed Si-OH group of hydrolysis reaction is selected from by exterior cooling control exothermic heat of reaction, controls the interpolation speed of acid catalyst and/or carry out the fs hydrolysis under the situation that does not have any organic cosolvent basically.

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