CN1984724A - Multi-layer coatings with an inorganic oxide network containing layer and methods for their application - Google Patents

Abstract

Multi-layer coatings are disclosed that include (1) a first layer comprising an inorganic oxide network, and (2) a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid composition that is hydrophilic and includes an essentially completely hydrolyzed organosilicate. Also disclosed are substrates coated with such multi-layer coatings, methods of applying such multi-layer coatings to a substrate and methods for improving the anti-fouling, self-cleaning, easy-to-clean, and/or anti fogging properties of an article.

Description

Have the laminated coating of the layer that contains inorganic oxide network and the method that applies them

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, 2004,438 rights and interests.

Invention field

The present invention relates to comprise the laminated coating of the ground floor and the second layer.These coatings are hydrophilic and durable, and demonstrate for example favourable property easy to clean, self-cleaning property, soil resistance, fog resistance, antistatic behaviour and/or antibacterium performance.In certain embodiments, this coating can become Superhydrophilic after the photoexcitation of catalysis material.

Background of invention

Hydrophilic coating is favourable for some application, for example needs to demonstrate soil resistance, property easy to clean, and self-cleaning property, and/or during the coating surface of 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, oil, dust, clay etc.For example, rainfall may be carried this pollutant.When rainwater when coating surface flows down, the surface that has deposited hydrophilic coating above can show antifouling property by preventing that pollutant in rainwater is attached on the surface.In addition, at fine day, the pollutant that air carries may contact and be attached to this surface with these surfaces.The surface that scribbles hydrophilic coating can be self-cleaning property and/or easy spatter property because when this surface contact water when (as in rainfall) this coating the ability of washing pollutant off is arranged.

Coating with self-cleaning property, property easy to clean and/or anti-scaling 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 pollutant and need not to use washing agent just can remove pollutant 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, can benefit from coating as windshield, glass pane, eyeglass lens, reflective mirror and other similar articles, 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 with anti-fogging performance.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 condensate particle is enough little so that their diameter when being visible wavelength only about half of, 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 condensate 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 hydrophily that is used for realizing them of the catalysis material in the siliceous base-material.For example, U.S. Patent No. 5,755,867 (" ' 867 patents ") disclose the graininess photochemical catalyst that is dispersed in the coating formation usefulness composition.Photochemical catalyst preferably is made up of the titanium dioxide granule with 0.1 micron or lower average grain diameter, wherein titanium dioxide can Detitanium-ore-type or the form of rutile-type use.Coating formation can form the coating of silicones with composition and be made up of the partial hydrolysis of hydrolyzable silane, the formed organopolysiloxane of polycondensation reaction subsequently when solidifying.In ' 867 patents, polysiloxane coating forms has sizable hydrophobicity with composition itself, but the photochemical catalyst by dispersion excite that can to give this water compatibility that is coated with layer height be hydrophily.

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 average grain diameter with 1-500 nanometer, hydrolyzable silicon compound.Hydrolyzable silicon compound is by general formula Si _nO _N-1(OR) _2n+1The alkyl silicate condensation product (wherein n is that 2-6 and R are the C1-C4 alkyl) of expression.This hydrolysate obtains with the hydrolysis percentage hydrolysis alkyl silicate condensation product 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 photochemical catalyst be dispersed in uncured or partly solidified polysiloxanes (organopolysiloxane) or its film forming component of precursor in.Photochemical catalyst can comprise the particle of metal oxide, as the anatase 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 photochemical catalyst, be bonded in film forming and under the photocatalysis of photochemical catalyst, replaced by hydroxyl with the organic group on the silicon atom of the polysiloxane molecule of composition.The surface of photocatalysis coating is " super hydrophiling " 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 the exciting of photochemical catalyst of disperseing.

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 hydrophiling of the coating that forms from said composition is that the photoexcitation by photochemical catalyst takes place, and film forming is not hydrophilic with material itself simultaneously.Therefore, before the exciting of photochemical catalyst, it is hydrophilic that coating is not considered to.

Yet, by be dispersed in catalysis material in the siliceous base-material be used for realize that there are some defectives in the hydrophilic prior art hydrophilic coating of coating.A remarkable shortcoming is that these coatings did not demonstrate hydrophily before the photoexcitation of photochemical catalyst.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 catalysis material.The coating that is disclosed in this ' 229 patent forms by applying the coating composition that contains silicones, and this silicones obtains as base-material and by hydrolysis and some four functionalized alkoxy silane of polycondensation.Coating composition also can comprise cabosil.Significantly, formed the filming of the composition from be disclosed in this ' 229 patent can be hydrophilic at first.Yet these initial hydrophilies it is believed that it is that the existence of cabosil in composition causes, rather than silicones itself possesses.It is believed that the silicones itself that is disclosed in this ' 229 patent is not hydrophilic, because desirable resin pH is 3.8-6.0, this shows that the Si-OR group is present in the resin to prevent gelation and hydrophilic amount.

Laminated coating advantageously is provided, and it comprises the coating that comprises inorganic oxide network and by hydrophilic and comprise the coating that the fluid composition deposition of the organosilicon acid esters of hydrolysis fully basically forms.

The accompanying drawing summary

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

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

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

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

Summary of the invention

In one aspect, the present invention relates to laminated coating, it comprises that (1) comprises the ground floor of inorganic oxide network, (2) second layer that applies at least a portion of ground floor, wherein the second layer is formed by at least a fluid composition deposition hydrophilic and that comprise the organosilicon acid esters of hydrolysis fully basically.

In yet another aspect, the present invention relates to laminated coating, it comprises that (1) comprises the ground floor of inorganic oxide network, (2) second layer that at least a portion of ground floor, applies, wherein the second layer is formed by at least a fluid composition deposition, said composition comprises (a) catalysis material and (b) hydrophilic and comprise the base-material of the organosilicon acid esters of hydrolysis fully basically.

In yet another aspect, the present invention relates to scribble the base material of laminated coating of the present invention.

Aspect another, the present invention relates to the method on the laminated coating paint base material, this method may further comprise the steps: (1) applies the ground floor that comprises inorganic oxide network on base material; (2) apply fluid composition at least a portion of ground floor, by the said composition deposition second layer, wherein the composition of the second layer is hydrophilic and comprises the organosilicon acid esters of hydrolysis fully basically; (3) solidify the second layer.

The invention still further relates to the method on the laminated coating paint base material, this method may further comprise the steps: (1) applies the ground floor that comprises inorganic oxide network on base material; (2) at least a portion of ground floor, apply fluid composition, on ground floor, deposit the second layer by said composition, wherein the fluid composition of the second layer comprises (a) catalysis material and (b) hydrophilic and comprise the base-material of the organosilicon acid esters of hydrolysis fully basically; (3) solidify the second layer.

The invention still further relates to the method for antifouling property, self-cleaning property, property easy to clean and/or the anti-fogging performance of improving goods, wherein these goods comprise the surface that deposits the coating that comprises inorganic oxide network, and this method comprises: (1) applies the fluid composition of the organosilicon acid esters that comprises basically hydrolysis fully on this surperficial at least a portion; (2) be solidificated in the fluid composition that applies in the step (1).

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 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 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 digits of report and adopt the ordinary technology of rounding off to explain.

Be similar to although express the number 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 fluid composition that comprises " catalysis material ".Quote for " catalysis material " this and to be meant the composition that comprises a kind of catalysis material and to comprise composition, as comprise the composition of two kinds of different catalysis materials more than a kind of catalysis 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 number 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 of a value 1 and the cited maximum 10,, has minimum of a value that is equal to or greater than 1 and the maximum that is equal to or less than 10 that is.

In one aspect, the present invention relates to laminated coating, it comprises that (1) comprises the ground floor of inorganic oxide network, (2) second layer that applies at least a portion of ground floor, wherein the second layer is by hydrophilic and comprise at least a fluid composition deposition of the organosilicon acid esters of hydrolysis fully basically.

Laminated coating of the present invention comprises the ground floor that comprises inorganic oxide network.Here the term of Shi Yonging " network " refers to the interconnected chain or the group of molecule.

In certain embodiments, the ground floor of laminated coating of the present invention is formed by the composition deposition that comprises colloidal sol, and this colloidal sol contains the alcoxylates of network formation with metal alkoxide thing such as alkoxy silane and/or another kind of metal such as zirconium, titanium and aluminium.If use, this alkoxy silane can be the organic group alkoxy silane, as alkylalkoxy silane or functional organic alkoxy silane.This alcoxylates can contain alkyl or aryl and can present dimer or more senior condensed forms, as long as hydrolyzable alkoxy grp keeps.

In certain embodiments, this network formation is general formula R with the metal alkoxide thing _xSi (OR ') _4-xAlkoxy silane, wherein R is an organic group, R ' is selected from low molecular weight alkyl such as methyl, ethyl, propyl group and butyl and x are integer and at least 1 and less than 4.The organic group of R for example can be especially, and alkyl, vinyl, methoxy ethyl, phenyl, γ-glycidoxy propyl group or γ-methacryloxypropyl comprise their mixture.This alcoxylates according to below the general reaction generation hydrolysis that provides, R wherein, R ' and x as mentioned above and y less than 4.

R _xSi(OR′) _4-x+yH ₂O→R _xSi(OR′) _4-x-y(OH) _y+yR ₂′OH

The condensation of the alcoxylates of hydrolysis is carried out according to general reaction

Or

Follow further hydrolysis and condensation.

In certain embodiments, the ground floor of laminated coating of the present invention can comprise other component, as the component of ultraviolet radiation absorber, organic film forming polymer and improvement flowing property, wearability and/or durability.Can be used for forming the composition of ground floor of laminated coating of the present invention and the non-limitative example of their production method and be described in US Patent No 4,753,827,4,754,012,4,799,963,5,035,745,5,199,979,6,042,737 and 6, in 106,605, they are hereby incorporated by reference.

In certain embodiments, the ground floor of laminated coating of the present invention is transparent.Here the term of Shi Yonging " transparent " is meant that cured coating does not change the percentage of the visible light that sees through transparent polymer base material that can applying coating basically.The pigmentable ability of coating is the function of the amount of the dyestuff that obtains under some qualifications of coating, and it is by the percentage expression quantitatively recently of the light that sees through the dyeing coating.The pigmentable ability of coating can be according in U.S. Patent No. 6,042,737, and on the 4th hurdle, the 57th row is to the 5th hurdle, and the method for describing in the eighth row is measured, and it is hereby incorporated by reference.

The example that is purchased composition of ground floor that is suitable for depositing laminated coating of the present invention is especially from PPG Industries, the Hi-Gard that Inc. is purchased ^TMWith SolGard  coating solution, from Essilor International, the Crizol  product that S.A. is purchased and from SDCTechnologies, the CrystalCoat that Inc. is purchased ^TMProduct.

Laminated coating of the present invention comprises the second layer at least a portion that is applied in ground floor, and wherein the second layer is formed by at least a fluid composition deposition of the organosilicon acid esters that comprises basically 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 silicon atom by oxygen atom.Suitable organosilicon acid esters comprises, without limits, contains by oxygen atom and is bonded in the organic group TMOS of four organic groups on the silicon atom and has the siloxane main chain ((Si-O) that is made of silicon atom _n) organic group oxygen radical siloxane.

In the organosilicon acid esters pass through oxygen atom be bonded on the silicon atom organic group without limits and can comprise, for example linear, branching or cyclic alkyl.The specific examples that oxygen atom is bonded in the organic group on the silicon atom of passing through in the organosilicon acid esters comprises, without limits, and methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, 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 group 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 bond among them.Among these organosilicon acid esters, the condensation product 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 group oxygen radical siloxane is the condensation product of above organic group TMOS.The condensation degree of organic group oxygen radical siloxane is restriction especially not.In certain embodiments, this condensation degree 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 the organic group TMOS class of monomer and the corresponding oligomer of condensation product 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 circulus 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 organosilicon acid esters that is used to deposit the fluid composition of the second layer is hydrolysis fully basically.Here the term of Shi Yonging " the organosilicon acid esters of hydrolysis fully basically " refers to a kind of like this material, and wherein the organic group oxygen base of organosilicon acid esters is substituted into by silanol group basically and makes this material become hydrophilic degree.Here the term of Shi Yonging " hydrophily " refers to that this material has compatibility 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, the composition that is used to deposit the second layer comprises the hydrolysis organosilicon acid esters that can form dry film, 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 polymers, 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.

The result, in certain embodiments of the invention, before can be used for depositing the photoexcitation of any catalysis material that can exist among the fluid composition of the second layer, laminated coating demonstrates the initial water contact angle that is no more than 20 °, or in some embodiments, is no more than 15 ° water contact angle, or, in another other embodiment, be no more than 10 ° water contact angle, as described below.Here Bao Dao water contact angle be by water droplet measure at the tangent line of the water droplet shape on the contact point and the measured value of the angle between the substrate surface, and by using by LordManufacturing, Inc. that make, that Gaertner Scientific goniometer optics is housed modified is caught bubble (captive bubble) indicator, measures by stopping (sessile drop) method of dripping.The surface that will measure is placed on horizontal level, 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 goniometer optical instrument that the circular protractor scale is housed.

Referring now to Fig. 1,, can see the figure that the FTIR that reflected the dry film that forms from this type of water wetted material analyzes.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 of hydrolysis fully basically that is included in the composition of the second layer that is used for depositing laminated coating of the present invention is the organosilicon acid esters and the product of the big hydrolysis of water gaging in the presence of the acid hydrolysis catalyst.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 group 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 catalyst.The specific examples of suitable catalyst comprises, without limits, and inorganic acid, example hydrochloric acid especially, sulfuric acid, nitric acid and phosphoric acid; Organic acid, especially as acetate, benzene sulfonic acid, toluenesulfonic acid, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, benzoic acid, phthalic acid, maleic acid, formic acid, citric acid, and oxalic acid; Base catalyst, as NaOH, potassium hydroxide, calcium hydroxide, ammonia; And organic amine compound, organo-metallic 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-aluminum compound, as three (acetopyruvic acid) aluminium, two (ethylacetoacetone acid) aluminium of single acetyl pyruvic acid, three (ethylacetoacetone acid) aluminium and ethylacetoacetone 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, the fluid composition that is used to deposit the second layer of laminated coating of the present invention also can comprise, outside dewatering, and organic solvent, 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, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, acetylacetone,2,4-pentanedione alcohols or the like.The specific examples of operable diol, derivatives comprises, without limits, and ethylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, propane diols, propylene glycol monomethyl ether, propane diols list ethylether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether 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, n-hexane or the like.The specific examples of operable ester comprises, without limits, and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, butyl-acetoacetate or the like.The specific examples of operable ketone comprises acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pentanedione or the like.The specific examples of operable ether comprises, without limits, and ether, butyl ether, methyl cellosolve, ethoxy ethanol, two  alkane, furans, oxolane or the like.

The material and their production method that are suitable in the fluid composition (depositing the second layer of laminated coating of the present invention by it) 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 non-limitative example that is purchased material that belongs to the organosilicon acid esters of hydrolysis fully basically and be suitable in the composition (depositing the second layer of laminated coating of the present invention by it) is can be from MitsubishiChemical Corporation, Tokyo, the MSH-200 that Japan obtains, MSH-400 and MSH-500 esters of silicon acis, with can be from Dainippon Shikizai, Tokyo, the Shinsui Flow MS-1200 esters of silicon acis that Japan obtains.

In certain embodiments, this base-material prepares in multi-stage method, wherein organic group TMOS (as previously mentioned in those any) and water react in the presence of acid hydrolysis catalyst (as previously mentioned in those any) in the phase I, and wherein the amount of water is lower than the stoichiometric amount of organic group oxygen base that can hydrolysis organic group TMOS.In certain embodiments, this acid hydrolysis catalyst comprises organic acid.In certain embodiments, water exists with 50% stoichiometric amount of organic group oxygen base that can hydrolysis organic group TMOS in the phase I.The result of phase I is the partial hydrolysis polycondensation product.

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

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

In another other embodiment, base-material prepares by the tetraalkoxysilane oligomer is initial, 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 group oxygen base that can the hydrolysis tetraalkoxysilane.

In certain embodiments, the amount of the organosilicon acid esters that exists in fluid composition (by the second layer of its deposit multilayer coating) is with the SiO in the organosilicon acid esters ₂Count 0.1-2wt%, as 0.2-0.90wt%, based on composition total weight.In these embodiments, the amount of organosilicon acid esters that can existence in fluid composition (by its deposition second layer) 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 organosilicon acid esters that exists in fluid composition (by the second layer of its deposit multilayer coating) decides by the performance that hope is incorporated in the composition.

In certain embodiments, laminated coating of the present invention comprises the second layer at least a portion that is applied in ground floor, wherein the second layer by comprise (a) catalysis material and (b) at least a fluid composition deposition of base-material form.In these embodiments, this base-material is hydrophilic and comprises the organosilicon acid esters of hydrolysis fully basically, as discussed above those.Here the term of Shi Yonging " base-material " refers to continuous material, and wherein the particle of catalysis material is dispersed in wherein.

In these embodiments, the second layer is formed by the fluid composition deposition that also comprises catalysis material except comprising the hydrophily base-material.Here the term of Shi Yonging " catalysis material " refers to by being exposed to radiation (as ultraviolet ray or visible radiation) and absorbing the material that radiation can photoexcitation.Catalysis material is a kind of like this material, and when being exposed to energy than in the conduction band and the higher light time of the energy gap between the valence band of crystal, 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, this catalysis material comprises metal oxide, as zinc oxide, and tin oxide, iron oxide, bismuth oxide, tungstic acid, strontium titanates, titanium dioxide, or their mixture.

In certain embodiments, at least a portion of catalysis material is present in the fluid composition that is used for depositing the second layer 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 average crystal diameter of particle can comprise cited value between any combination of cited value.It will be understood by those skilled in the art that the performance that the average crystal diameter of particle can be incorporated in the second layer with hope is that the basis is selected.In some embodiments, whole basically catalysis material is present in the composition that is used for depositing the second layer with the form of this type of particle.The average crystal diameter of photocatalysis metal oxide particle can be measured by SEM or transmission electron microscope, and the crystalline phase of this type of particle can be measured by X-ray diffraction, and is known as those skilled in the art.

As mentioned above, some material by for example be exposed to ultraviolet ray (" UV ") and/or visible radiation and absorption they the time can photocatalysis.In certain embodiments, the catalysis material of existence comprises and can carry out the material of photoexcitation by in these mechanism one or more.Can be used as the part of fluid composition (depositing the second layer of laminated coating of the present invention) and light-catalysed examples of material comprises by being exposed to ultraviolet radiation by it, without limits, tin oxide, zinc oxide, and the brockite of titanium dioxide, anatase and rutile form.Can be used as the part of fluid composition (depositing the second layer of laminated coating of the present invention) and light-catalysed examples of material comprises by being exposed to visible radiation by it, without limits, the brockite form of titanium dioxide, carry out the titanium dioxide of chemical modification via the flame pyrolysis of Titanium, the titanium dioxide that nitrogen mixes and the titanium dioxide of plasma treatment.

In certain embodiments, this catalysis material provides with the solation (as the TiO 2 sol form) that comprises the particle that is dispersed in the catalysis material in the water.This type of colloidal sol is commercially available easily from market.Be suitable for comprising as this type of examples of material of the part of fluid composition (depositing the second layer of laminated coating of the present invention) by it, without limits, can be from the S5-300A and the S5-33B of Millenium Chemicals acquisition, can be from the STS-01 of IshiharaSangyo 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, this catalysis material exists with the form of the colloidal sol of the mixture 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 particle.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, this catalysis material comprises chemical modification titanium dioxide.This type of examples of material comprises by people such as Khan, Efficient Photochemical WaterSplitting by a Chemically Modified n-TiO ₂Science Reprint, 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 2002/0169076A1, 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 plasma treatment of describing in the 49th row-Di 7 hurdles, 343, the 2 hurdles the 17th row.

In certain embodiments, the amount of the catalysis material that exists in fluid composition (by the second layer of its deposit multilayer coating) 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.In these embodiments, the amount of the catalysis material that can exist can be between any combination of cited value, comprises cited value.The amount that it will be understood by those skilled in the art that the catalysis material that exists in fluid composition (by the second layer of its deposit multilayer coating) decides by the performance that hope is incorporated in this layer.

In certain embodiments, the organosilicon acid esters of this catalysis material and hydrolysis fully basically was 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 0.2: 0.6 (by weight) is present in the fluid composition (by its deposition second layer).In these embodiments, the ratio of catalysis material and organosilicon acid esters can comprise cited value between any combination of cited value.The ratio that it will be understood by those skilled in the art that catalysis material and organosilicon acid esters in the composition of the second layer is decided by performance such as the desired refraction index that has of composition (it is by deciding with reference to the base material that applies composition) that hope is incorporated in this layer.

In certain embodiments, this fluid composition (depositing the second layer of laminated coating of the present invention by it) 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 assessing the antistatic effect of this material is to measure the surface resistivity of material.In certain embodiments, the base-material of the composition of the second layer 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 not more than 1.0 * 10 ¹⁰Ohm/cm ²Surface resistivity.Here Bao Dao surface resistivity can be used ACL Statitide Model800 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 the probe on the plate of this instrument of 2.75 inches measure.As a result, the invention still further relates to the laminated coating with second layer, this second layer has this type of antistatic property.

In certain embodiments, this fluid composition (depositing the second layer of laminated coating of the present invention by it) can further comprise inorganic particle, silica for example, alumina comprises and handles alumina (for example silica-processing alumina is called alpha-aluminium oxide) interior, carborundum, diamond dust, cube shaped boron nitride, and boron carbide.This type of inorganic particle can for example be colourless basically, as silica, and cabosil for example.This type of material can provide the mar-proof and anti-zoned property of enhancing.This type of particle can have from sub-micron (for example nano-sized particles) to 10 microns particle mean sizes, and this depends on the final application and the desired effect of composition.

In certain embodiments, in being introduced in fluid composition before, this type of particle comprises the inorganic particle of the particle mean size with 1-10 micron or 1-5 micron.In other embodiments, in being introduced in fluid 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 particle mean size between 50 nanometers as 1 nanometer.In some embodiments, in being introduced in fluid composition before, inorganic particle has the 5-50 nanometer, or the particle mean size of 5-25 nanometer.Granularity can comprise this enumerator between any combination of these values.

In certain embodiments, this particle can be with 5.0wt% at the most, or from 0.1-1.0wt%; Or be present in the fluid composition (by the second layer of its deposit multilayer coating), based on the gross weight of composition from the amount of 0.1-0.5wt%.The amount of the particle that exists in fluid composition can comprise this enumerator between any combination of these values.

In certain embodiments, this fluid composition (by the second layer of its deposit multilayer coating) also comprises antimicrobial reinforcing material, for example metal; As silver, copper, gold, zinc, their compound, or their mixture; Quaternary ammonium compound, as benzalkonium chloride, dialkyl dimethyl ammonium chloride, softex kw, cetylpyridinium chloride, and 3-(trimethoxysilyl)-propyl-dimethyl-octadecyl-ammonium chloride; Phenols, as 2-benzyl-chlorophenol, o-phenyl phenol, neighbour-phenylphenol sodium, pentachlorophenol, 2 (2 ', 4 '-dichlorophenoxy)-5-chlorophenols and 4-chloro-3-methylphenol; Halogen compounds is as TCCA salt, DCCNa, DCCK, single TCCA salt, DCCK, 1: 4 dichlorodimethylhydantoin, bromo-chloro-dimethyl hydantoin, 2,2 '-two bromo-3-nitrilo-propionamides, two (1,4-acetyl bromide oxygen base)-2-butylene, 1,2-two bromo-2,4-dicyanobutane, 2-bromo-2-nitropropane-1,3-glycol and bromoacetic acid benzyl ester; Organo-metallic compound, as 10, the two phenoxy group-arsines of 10 '-oxo, tributyl tin oxide, tributyl tin fluoride, copper 8-quinolinolate, copper naphthenate, chromated copper arenate, arsenic acid cuprammonium, and cuprous oxide; Organosulfur compound, as di-2-ethylhexylphosphine oxide thiocyanates (MBT), ethenylidene Rhodan ester, chlorethylidene Rhodan ester, SDD, ethylenebis aminodithioformic acid disodium, PZ 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) benzimidazole, N-(trichloromethyl sulfenyl)-4-cyclohexene-1,2-dicarboximide, N-(trichloromethyl sulfenyl)-phthalimide 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]-ethylenediamine, 2-(methylol) amino-ethanol, 2-(methylol) amino-2-methyl propyl alcohol, 2-methylol-2-nitro-1, ammediol, six hydrogen-1,3,5-three-(2-ethoxy)-s-triazine, six hydrogen-1,3,5-triethyl group-s-triazine, 4-(2-nitro butyl) morpholine+4,4 '-(2-ethyl-2-nitro-trimethylene)-dimorpholine, glutaraldehyde, 1,3-dihydroxymethyl-5,5-dimethyl-hydantoins, and imidazolidinyl urea and their mixture.

In certain embodiments, the fluid composition that is used to deposit the second layer comprises the antimicrobial of the consumption of the effect that is enough to demonstrate opposing microorganism and various especially Mycophytas.More particularly, in certain embodiments, the second layer of laminated coating of the present invention can deposit from fluid composition, and said composition contains the antimicrobial that is enough to be suppressed at the consumption of growth of microorganism 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, the amount of the microbial resistance reinforcing material that exists at the fluid composition that is used for depositing the second layer 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%.The amount of the microbial resistance reinforcing material that can exist in fluid composition in these embodiments, can be between any combination of the above value of enumerating (comprising cited value).

In certain embodiments, this fluid composition (depositing the second layer of laminated coating of the present invention by it) can comprise the optical activity reinforcing agent, as platinum, and gold, palladium, iron, nickel, or its soluble-salt.The known redox active that can strengthen photochemical catalyst of the interpolation of these materials in comprising the composition of catalysis material promotes to be attached to the decomposition of the pollutant on the coating surface.In certain embodiments, the amount of the optical activity reinforcing agent that exists in fluid composition (by the second layer of its deposit multilayer coating) is 0.01-1.0wt%, as 0.1-1.0wt%, or, in other embodiments, 0.1-0.5wt% is based on the gross weight of composition.In these embodiments, the amount of the optical activity reinforcing agent that can exist can be between any combination of cited value, comprises cited value.In certain embodiments, fluid composition (depositing the second layer of laminated coating of the present invention by it) can comprise coupling agent, and the latter for example improves the cohesive of the second layer to ground floor.The example that is suitable for the coupling agent of this purpose 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, the amount of the coupling agent that exists in fluid composition (by the second layer of its deposit multilayer coating) 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 can exist in fluid composition can be between any combination of the above value of enumerating, and comprises cited value.

In certain embodiments, fluid composition (depositing the second layer of laminated coating of the present invention by it) can comprise surfactant, and when composition was applied on the ground floor, this surfactant for example assisted to improve the wettability of composition.The example that is suitable for the surfactant 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, the 46th goes to the 40th hurdle, the material of determining in the 39th row, and the both is hereby incorporated by reference.

In certain embodiments, the amount of the surfactant that exists in fluid composition (by the second layer of its deposit multilayer coating) is 0.01-3wt%, as 0.01-2wt%, or, in other embodiments, 0.1-1wt% is based on the gross weight of the solid in the composition.In these embodiments, the amount of the surfactant that can exist in fluid composition can be between any combination of the above value of enumerating, and comprises cited value.

In certain embodiments, this fluid composition (by the second layer of its deposit multilayer coating) also comprises cleaning combination.Suitable cleaning combination comprises some materials like this, and the latter comprises surfactant, dicyandiamide solution, water and pH conditioning 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 dicyandiamide solution, and this dicyandiamide solution comprises low boiling point solvent, as isopropyl alcohol and middle high boiling solvent, as has the C of 3-8 carbon atom altogether ₁-C ₄The aklylene glycol alkyl ether.Suitable be purchased that cleaning combination comprises can be from SC Johnson and Son, the WINDEX  that Inc. is purchased.As a result, certain embodiments of the present invention relate to fluid composition, and the latter is hydrophilic and comprises (a) organosilicon acid esters and (b) cleaning combination of hydrolysis fully basically.Some embodiment of this based composition also comprises catalysis material.

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

If necessary, this fluid composition (depositing the second layer of laminated coating of the present invention by it) can comprise known other the optional coating of paint field technical staff.

This fluid composition (depositing some embodiment of the second layer of laminated coating of the present invention by it) can be by prepared in various methods.In some cases, composition is by being prepared as follows: the water wetted material of the organosilicon acid esters that comprises basically hydrolysis fully (i) is provided, and wherein the pH of water wetted material is no more than 3.5; (ii) provide to comprise colloidal sol or the slurry that is dispersed in the catalysis material in the diluent, wherein the pH of colloidal sol is no more than 3.5; (iii) the water wetted material that will provide in (i) mixes so that catalysis material is dispersed in the water wetted material with colloidal sol that provides in (ii) or slurry.Having been found that the fluid composition that is made by this method can be stablized surpasses 12 months and few or do not have coalescent or precipitation.Here Bao Dao pH value can use the ACCUMET pH meter that is purchased from FisherScientific to measure.

In some cases, the fluid composition that is used to deposit the second layer of laminated coating of the present invention is produced by the hydrophilic 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, or in some cases, be 1.3 to 3.5, or under another other situation, be 3.0 to 3.5.In certain embodiments, this hydrophilic material is by at first providing basically the organosilicon acid esters of hydrolysis fully, wherein the pH of hydrophilic material is greater than required pH, then acid is added to the pH until hydrophilic material is no more than 3.5 in the hydrophilic material, or be 1.3 to 3.5 in some cases, or under another other situation, 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 Shinsui Flow MS-1200 esters of silicon acis, and they are typically provided under 3.5 to 4.5 pH by supplier.

In certain embodiments, before adding acid, this hydrophilic material can be used diluent such as water or organic solvent diluting, for example reduces the solids content of hydrophilic material, allows to form thin film thus.

The acids of regulating its pH in the hydrophilic material be can add to and inorganic 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, dichloroacetic acid, trifluoroacetic acid, benzene sulfonic acid, toluenesulfonic acid, xylene monosulfonic acid, ethyl phenenyl azochlorosulfonate acid, benzoic acid, phthalic acid, maleic acid, formic acid and oxalic acid.

In some cases, the fluid composition that is used for the second layer of deposit multilayer coating is produced by the colloidal sol or the slurry that comprise the catalysis material that is dispersed in diluent are provided, wherein the pH of colloidal sol or slurry is no more than 3.5, or in some cases, be 1.3 to 3.5, or under another other situation, be 3.0 to 3.5.In certain embodiments, the pH of colloidal sol or slurry is substantially the same with the pH of hydrophilic material.In certain embodiments, 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 in some cases, be 1.3 to 3.5, or till being 3.0 to 3.5 under another other situation and final the acquisition.For example; as previously mentioned; the catalysis material that is used for some embodiment of fluid composition (depositing the second layer of laminated coating of the present invention by it) can comprise the colloidal sol of the titanium dioxide that is purchased with trade name NTB-1 and/or NTB-13 from Showa DenkoCorporation, and wherein this colloidal sol comprises the brookite type titanium dioxide particle that is dispersed in the water or the mixture of brookite type and Detitanium-ore-type and/or rutile titanium dioxide particle.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 catalysis material or the slurry to and as previously described inorganic acid and organic acid comprised.In certain embodiments, add to the colloidal sol that comprises catalysis material or the acid in the slurry be with the water wetted material that adds to as previously described in same acids.

Be used to deposit hydrophilic material that the fluid composition of the second layer of laminated coating of the present invention can provide by method as mentioned above and mix, catalysis material is dispersed in the hydrophilic material and makes with colloidal sol or the slurry that method as mentioned above provides.This blend 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 catalysis material in hydrophilic material.As a result, certain embodiments of the present invention relate to laminated coating, and wherein the second layer is no more than 3.5 by having, as 1.3 to 3.5, or, in some cases, the fluid composition of 3.0 to 3.5 pH deposition.

In other cases, fluid composition (depositing the second layer of laminated coating of the present invention by it) is by being prepared as follows: the hydrophilic material of the organosilicon acid esters that comprises basically hydrolysis fully (i) is provided, and wherein the pH of hydrophilic material is 7.0-8.5; (ii) provide to comprise colloidal sol or the slurry that is dispersed in the catalysis material in the diluent, wherein the pH of colloidal sol or slurry is 7.0-8.5; (iii) the hydrophilic material that will provide in (i) mixes so that catalysis material is dispersed in the hydrophilic material with colloidal sol that provides in (ii) or slurry.

In some cases, composition (depositing the second layer of laminated coating of the present invention by it) is produced by the hydrophilic material that the organosilicon acid esters that comprises basically hydrolysis fully is provided, wherein the pH of hydrophilic material is 7.0 to 8.5, as 7.0 to 8.0 or in some cases, is 7.5 to 8.0.In certain embodiments, this hydrophilic material is by at first providing basically the organosilicon acid esters of hydrolysis fully, wherein the pH of hydrophilic material is lower than required pH, then alkali being added in the hydrophilic material until the pH of hydrophilic material is 7.0-8.5, as 7.0-8.0, or in some cases, be till the 7.5-8.0 and final the acquisition.

In certain embodiments, before adding alkali, this hydrophilic material can be used diluent such as water or organic solvent diluting, for example reduces the solids content of hydrophilic material, allows to form thin film thus.

The material of regulating its pH in the hydrophilic material be can add to and organic base and inorganic base comprised.The specific examples of alkali that can be used for improving the pH of hydrophilic material comprises, without limits, alkali metal hydroxide, as NaOH, potassium hydroxide and lithium hydroxide; Ammonium hydroxide; Quaternary ammonium hydroxide is as tetraethyl ammonium hydroxide and hydroxide tetraethoxide ammonium; Ammonia; Amine such as triethylamine and 3-(diethylamino)-propane-1-alcohol; Hydroxide uncle sulfonium is as trimethyl hydroxide sulfonium and triethyl group hydroxide sulfonium; Quaternary phosphonium hydroxides  such 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; Sodium metasilicate; Carbonic hydroammonium; With their mixture.

In some cases, this fluid composition (depositing the second layer of laminated coating of the present invention by it) comprises that by providing the colloidal sol or the slurry that are dispersed in the catalysis material in the diluent prepare, wherein the pH of colloidal sol or slurry is 7.0 to 8.5, as 7.0 to 8.0, or in some embodiments, be 7.5 to 8.0.In certain embodiments, the pH of colloidal sol or slurry is substantially the same with the pH of hydrophilic material.In certain embodiments, 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 alkaline matter 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 cases and final the acquisition.

Alkali with the pH that regulates it be can add in the colloidal sol that comprises this catalysis material or the slurry to and as previously described inorganic base and organic base comprised.In certain embodiments, add to the colloidal sol that comprises catalysis material or the alkali in the slurry be with add described water wetted material in identical alkali.

Being used for depositing colloidal sol that hydrophilic material that the fluid composition of the second layer of laminated coating of the present invention can provide by method as mentioned above and method as mentioned above provide or slurry mixes and catalysis material is dispersed in hydrophilic material makes.This blend 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 catalysis material in hydrophilic material.As a result, certain embodiments of the present invention relate to laminated coating, and wherein the second layer is by having 7.0 to 8.5, as 7.0 to 8.0, or the fluid composition deposition of 7.5 to 8.0 pH in some cases.

Referring now to Fig. 2 and 3,, can find respectively (i) laminated coating of the present invention the second layer some embodiment magni-scale schematic cross-sectional view and the microphoto of embodiment of the second layer of laminated coating of the present invention (ii) has been described.Find out that from Fig. 2 and 3 in certain embodiments, the second layer of laminated coating of the present invention is deposited by fluid composition, wherein catalysis material is dispersed in the whole hydrophily base-material.In these embodiments, the second layer of laminated coating comprises that the catalysis 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 hydrophily base-material 20 relatively.Especially, as shown in Figure 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 catalysis material colloidal sol or slurry before their blending, make coalescent the prevention that this has obtained the fluid composition of low turbidity.Therefore, in certain embodiments of the invention, the second layer of laminated coating is by the fluid composition deposition with low turbidity.

Fluid composition (depositing the second layer of laminated coating of the present invention by it) and/or an advantage of producing their method are that they can form stable single packing liquid composition.Therefore, in certain embodiments, the second layer of laminated coating of the present invention is deposited by single packing liquid composition.Here the term of Shi Yonging " single packing liquid composition " refers to a kind of like this fluid composition, and each component that wherein constitutes this fluid composition is stored in single container together.

The single packing liquid composition that can be used for being formed on the second layer in the laminated coating of the present invention comprises at least two kinds of components, comprises the catalysis material and the hydrophily base-material of previous discussion.In addition, this type of single packing liquid composition has at least 3 months shelf-life.Here the term of Shi Yonging " shelf-life " refers to when each component blending is in single container and precipitation or the cohesion time span between having occurred to when the composition turbidity increases the degree that makes composition no longer can form the low haze film.In certain embodiments, single packing liquid composition has at least 3 months shelf-life, or in some other embodiment, at least 6 months, or, in some cases, at least 12 months shelf-life.

In certain embodiments, this fluid composition (depositing the second layer of laminated coating of the present invention by it) was at 3 months, 6 months or have the turbidity that is no more than 600NTU 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 nephelometer 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, the second layer of laminated coating of the present invention has low haze.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 nephelometers, and as from Pacific Scientific Company, the Hazegard  Model No.XL-211 that Silver Spring, Md are purchased measures.

The invention still further relates to the method on the laminated coating paint base material, this method may further comprise the steps: (1) applies the ground floor that comprises inorganic oxide network on base material; (2) apply fluid composition at least a portion of ground floor, by the said composition deposition second layer, wherein the composition of the second layer is hydrophilic and comprises the organosilicon acid esters of hydrolysis fully basically; (3) solidify the second layer.

In these methods, the composition that ground floor comprises inorganic oxide network and is used for depositing this layer can be applied over base material by for example spraying of any method, roller coat, dipping, spin coating, flow coat, brushing and the wiping method of using at coating technology.After applying, this based composition can solidify.For example, composition (by the ground floor of its deposit multilayer coating) can be used as the solution of solid in suitable solvent such as water, organic solvent or their mixture and is applied on the base material.Then can evaporating solvent and coating by being heated to high temperature, reach 1 to 16 hour as 80 to 130 ℃ and solidify.

In these methods of the present invention, this fluid composition (by it the deposition second layer) can by any method of using in the coating technology as mentioned above method be applied on the base material.

In these methods of the present invention, after the second layer is applied on the ground floor, the second layer is solidified, promptly dry.Though be not bound by any theory, it is believed that some silanol group generation condensations of the base-material of hydrolysis fully make to have formed the Si-O-Ti key in composition basically after solidifying.It is believed that the existence of these groups has strengthened the durability of the second layer among laminated coating of the present invention, such as will be described below in more detail.

Fluid composition (depositing the second layer of laminated coating of the present invention by it) can be the self-curing type, makes composition to be cured under the help without any curing catalysts.In addition, this fluid composition (depositing the second layer of laminated coating of the present invention by it) can for example solidify at ambient temperature.In other words, the curing of the fluid composition of the second layer can be placed in air by said composition, and promptly the air drying is finished.According to certain embodiments of the present invention, this fluid composition solidifies by following manner: allow it be exposed to air under 25 ℃ and reach 2-3 hour and obtain Superhydrophilic and reach 16 hours to obtain long durability.This type of fluid composition also can solidify by heat drying.For example, according to certain embodiments of the present invention, the second layer reaches 3-5 minute by allowing it be exposed to air, forces its drying to be cured at least 3 seconds under 80 ℃ to 100 ℃ then.

Laminated coating of the present invention can be applied over polymer, pottery, concrete, cement, glass, timber, paper or metal base, and their composite, or other material are comprising the base material of japanning.In some specific embodiments, laminated coating of the present invention can be applied on the polymeric substrate.In certain embodiments, this type of polymeric substrate can comprise the solid material of solid transparent or optically clear, and as in U.S. Patent No. 6,042,737, the 6 hurdles, the 66th row are to the 8th hurdle, those disclosed in the 34th row, and the document is hereby incorporated by reference.In certain embodiments, this type of polymeric substrate can comprise photochromic material, and as in U.S. Patent No. 6,042,737, the 8 hurdles, the 35th row are to the 10th hurdle, those disclosed in the 19th row, and this patent is hereby incorporated by reference.

The specific examples that can apply the goods of laminated coating of the present invention thereon comprises, without limits, and window; In carplane, the windshield on the ship etc.; Indoor and outdoor reflective mirror; Lens, glasses or other optical instrument; The sports goggles of protectiveness; Mask; Faceplate; The glass slide plate of frozen food display con-tainer; Cloche; The building wall; The building roof; Outside ceramic tile on building; Building stone; The steel plate of japanning; 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, permanent plant and other goods; Air handling system and clarifier; Kitchen and bathroom internal equipment and equipment; Ceramic tile; Air filter; The store display cabinet; Computer display; Heat exchanger of air condition; High-tension cable; The interior external member of building; Glass pane; Tableware; Living space, bathroom, kitchen, hospital room, factory floor space, office space or the like wall; Sanitary apparatus is as washbowl, bathtub, w.c.pan, urinal, sink or the like; And electronic equipment, as computer display.

In certain embodiments, this fluid composition (depositing the second layer of laminated coating of the present invention by it) can have extremely low solids content, and about 1wt% total solid is based on the gross weight of composition.Therefore, this type of fluid composition can apply with extremely little film thickness.Especially, according to certain embodiments of the present invention, this fluid composition is to be no more than 200 nanometers (0.2 micron), or in some embodiments with 10 to 100 nanometers (0.01 to 0.1 micron), the form of film with the build of 20 to 60 nanometers (0.02 to 0.06 micron) in another other embodiment of the present invention is applied at least a portion of ground floor.The coating of the second layer of laminated coating of the present invention under this low film thickness can particularly advantageously provide optical thin film, and the refraction index of refraction index that will composition and ground floor mates.

As previously described, fluid composition (depositing the second layer of laminated coating of the present invention by it) is hydrophilic at first, that is, after applying and before the exciting of any photochemical catalyst that can exist in the composition of the second layer, the second layer demonstrates the affinity to water.This initial hydrophily can be being no more than 20 ° or in some embodiments being no more than 15 °, or, in another other embodiment, represent with the initial water contact angle that is no more than 10 °.By exciting of catalysis material (if the change that has), the second layer of laminated coating of the present invention can be given " Superhydrophilic ", that is, and and after the exciting of photochemical catalyst, the second layer of laminated coating of the present invention can demonstrate and be lower than 5 °, even little water contact angle to 0 °.

The mode that can be used for exciting light catalyst (if any) is present in the fluid composition that is used for depositing the second layer, and this depends on the catalysis material that uses in composition.For example, the light activated material by being exposed to visible light, as the brockite form of titanium dioxide, and the titanium dioxide of nitrogen or carbon doping, can be exposed to any visible light source, comprise any radiation of at least 400 nano wave lengths.On the other hand, the anatase of titanium dioxide and rutile form, tin 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 UV ray radiation source that is used for this type of photochemical catalyst 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 28 watts of/square metre (W/m on coating surface ²) intensity.

In certain embodiments, laminated coating 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, laminated coating of the present invention reaches and became Superhydrophilic in 1-2 hour by being exposed to sunshine.Perhaps, laminated coating 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, laminated coating of the present invention can especially demonstrate very favorable hydrophily, antistatic property and/or antibacterium performance.Because they are hydrophilic, laminated coating of the present invention can demonstrate favourable self-cleaning property, soil resistance, and/or anti-fogging performance.Therefore the invention still further relates to the method for antifouling property, self-cleaning performance, property easy to clean and/or the anti-fogging performance of improving goods, wherein these goods comprise the surface that has deposited the coating that comprises inorganic oxide network, and this method comprises: (1) applies the fluid composition of the organosilicon acid esters that comprises basically hydrolysis fully at least a portion on surface; (2) be solidificated in the composition that applies in the step (1).

Another feature of laminated coating of the present invention is that they can obtain the durable especially second layer.The surprising durability of this type coating can be passed the ability of keeping contact angle in time according to the film surface and be measured under the weathering condition that quickens.In time can be few more after passing or several wiping cycles by the contact angle that institute's test specimen is kept, film is durable more.The simulation weathering of film can be obtained by the weathering chamber, and it comprises Cleveland condensation cabinet (CCC) and QUV exerciser (Q-Panel Company, Cleveland, the product of Ohio).

In certain embodiments, this catalysis 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 laminated coating be present in the fluid composition (depositing the second layer of laminated coating of the present invention) by it, wherein CCC chamber operation under the steam temperature of 140  (60 ℃) in indoor environment causes the constant water condensation on testing surface.In fact, illustrated as the embodiment here, found with the hydrophily base-material that contains here that type of describing but do not have the composition of catalysis material to compare, in some embodiment of this based composition, comprised catalysis material and the coating that produces demonstrates improved significantly durability.Illustrated as Fig. 4, in certain embodiments, this catalysis 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 laminated coating be included in the composition (depositing the second layer of laminated coating of the present invention by it), and do not exist catalysis material to obtain after approximately 2000-3000 hour exposure, 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 catalysis material.Do not wish to be bound by any theory, the inventor believes that this surprising result can form the Si-O-Ti key owing to the partial cross-linked of catalysis material and organosilicon acid esters in coating.The inventor believes, some catalysis materials have participated in that this is crosslinked, and some catalysis materials in addition after CCC exposes 4000 hours still maintenance can be used for light-catalysed activity.

In certain embodiments, laminated coating of the present invention can be in the QUV exerciser that fluorescent tube (B313 nanometer) is housed be kept the contact angle of 5-6 degree after 4 hours in exposure 650 hours under 65-70 ℃ the blackboard temperature with 50 ℃ of following condensation humidity.

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 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 pure, dry 1 liter of glass beaker.Solution A (～0.20 mole H with 3.6 grams ₂O) add at leisure among the TMOS, 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 retention 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 wetability when on breadboard, applying, do not had the optics flaw, and passed through to keep simultaneously for 50 flushing/arid 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 absolute methanols (cosolvent) of 3.6 grams add in pure, dry 1 liter of glass beaker.Solution A (～0.20 mole H with 3.6 grams ₂O) add at leisure in the TMOS solution, by the interpolation speed control 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 retention 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.

On breadboard, apply demonstration dewetting problem with above solution, and spottiness.Result of the test shows, thereby comprising of cosolvent guaranteed that more effective hydrolysis and corresponding condensation form the more oligomer of HMW, 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 pure, dry 1 liter of glass beaker.Solution A (～0.20 mole H with 3.6 grams ₂O) add at leisure among the TMOS, by the interpolation speed control 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 retention 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.Allow 1%SiO ₂The under agitation abundant hydrolysis of base-material solution is spent the night.

On breadboard, apply demonstration dewetting problem with above solution, and spottiness.Result of the test shows, by do not control thermal discharge and allow hydrolysis temperature reach～40 ℃, will cause the much higher condensation of degree and form the more oligomer of HMW, 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 esters of silicon acis 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 esters of silicon acis 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-fluid composition

Fluid composition A-G in table 1 is prepared as follows.In being housed, 1 liter of glass container 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, the pH of mixture is adjusted to 1.8.

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, by under agitation adding 2N hydrochloric acid till reaching required pH, pH is adjusted to 1.8 then.The II that feeds intake under agitation is added among the I that feeds intake then, produces hydrophilic compositions A-G.

Table 1

Composition	Esters of silicon acis/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 with Windex  spraying, and dries with paper handkerchief (the Kaydry  that is purchased from Kimberly-Clark Corp.).

The fluid 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 is then by allowing wet pad contact and to be applied with straight, overlapping a little road (strokes) with the glass test substrate.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.

Endurancing-test 1

The test substrate that scribbles fluid composition A and B is placed in the Cleveland condensation chamber of operation under 140  (60 ℃).Each test substrate jede Woche 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 indicator is caught in Inc. improvement that make, that Gartner Scientific goniometer optical element is housed, measures by stopping the method for dripping.The surface that will measure is placed on horizontal level, 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 goniometer farsighted glasses that the circular protractor scale is housed.The result is summarised in the table 3.

Table 3

	Composition A		Composition B
					Hourage 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

Endurancing-test 2

The durability of test substrate that scribbles fluid composition A-G is tested but measured water contact angle before in putting into the Cleveland condensation 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

Endurancing-test 3

Scribble composition of the present invention test substrate durability also with scribble the base material that comprises hydrophilic organic silicon acid esters base-material but do not contain the composition of catalysis 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 condensation chamber, 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-fluid composition

Prepare fluid composition H and I according to the mode of describing in embodiment 6, 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 durability of these compositions is analyzed according to the mode of describing in endurancing-test 1 then.The results are shown in Table 6.

Table 5

Composition	Esters of silicon acis/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
					Hourage 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-fluid composition

Prepare fluid composition K, L, M and O according to the mode of describing in embodiment 6, different is that pH is adjusted to value and the base-material/TiO that lists in table 7 ₂Weight ratio is according to regulating shown in the table 7.Prepare fluid 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 fluid composition among the I that feeds intake.The haze values of these compositions is passed through then by ShabanManufacturing Inc, the nephelometer 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	Esters of silicon acis/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 conating (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 air drying in advance.These lens carry out plasma treatment 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 recovery rate (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 pollution resistance of the embodiment 11-rubble of anti-automobile dust

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 wash-bottle to apply Hi-Gard regional 2 by the curtain coating method ^TM1080 (from PPG Industries, the coating solution that contains organosilan that Inc. is purchased), dry 5 minutes of air and in 240  (116 ℃) baking 3 hours down.With above described the same for regional #2, zone 3 is coated with Hi-Gard 1080.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 air then is dry and from condensation.With above described the same for zone 2, zone 4 is coated with Hi-Gard 1080.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 cleannes.After using from the gardening usefulness water rinse of flexible pipe, the cleannes of the regional 1-5 of wheel #1 are measured according to the scale of 1-10, and higher numerical value reflection is than clean Surface.The results are shown in the table 8.

Table 8

The zone	Cleannes
		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 wash-bottle 2 to apply SolGard  330 coating (from PPG Industries, the coating solution that contains organosilan that Inc. is purchased) in the zone, dry 5 minutes of air 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-Gard 1080.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 air then is dry and from condensation.With above described the same for zone 2, zone 4 is coated with Hi-Gard 1080.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 cleannes.After using from the gardening usefulness water rinse of flexible pipe, the cleannes of the regional 1-5 of wheel #1 are measured according to the scale of 1-10, and higher numerical value reflection is than clean Surface.The results are shown in the table 9.

Table 9

The zone	Cleannes
		1	2
2	8
		3	10
4	10
		5	10

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 their wording statement clearly in addition.Therefore, embodiment described in detail here only is to illustrate not limit the scope of the invention, and scope of the present invention provides whole width by claims and all equivalency range thereof.

Claims (37)

1. laminated coating comprises:

(1) comprise inorganic oxide network ground floor and

(2) be applied in the second layer at least a portion of ground floor, wherein the second layer is formed by at least a fluid composition deposition hydrophilic and that comprise the organosilicon acid esters of hydrolysis fully basically.

2. the laminated coating of claim 1, wherein ground floor is formed by the composition deposition that comprises colloidal sol, and this colloidal sol contains network and forms with the metal alkoxide thing.

3. the laminated coating of claim 2, wherein this network forms and comprises general formula R with the metal alkoxide thing _xSi (OR ') _4-xAlkoxy silane, wherein R is an organic group, R ' is that to be selected from alkyl in methyl, ethyl, propyl group and the butyl and x be integer and less than 4.

4. the laminated coating of claim 1, wherein ground floor is transparent.

5. the laminated coating of claim 1, the fluid composition that wherein is used to deposit the second layer further comprises catalysis material.

6. the laminated coating of claim 5, wherein average crystal diameter is the 3-35 nanometer.

7. the laminated coating of claim 5, wherein this catalysis material be selected from brookite type titanium dioxide, carry out the titanium dioxide of chemical modification, titanium dioxide, plasma treatment titanium dioxide and their mixture that nitrogen mixes by flame pyrolysis.

8. the laminated coating of claim 5, wherein this catalysis material is present in the fluid composition with the amount of 0.1-0.75wt%, based on the gross weight of composition.

9. the laminated coating of claim 1, the organosilicon acid esters that wherein is used to deposit the fluid composition of the second layer is selected from organic group TMOS, organic group oxygen radical siloxane and their mixture, and wherein this organic group 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.

10. the laminated coating of claim 1, wherein the organosilicon acid esters is to press SiO ₂The amount of meter 0.1-2wt% is present in the fluid composition that is used for depositing the second layer, based on the gross weight of composition.

11. the laminated coating of claim 1, the pH that wherein is used to deposit the fluid composition of the second layer is no more than 3.5.

12. the laminated coating of claim 1, the pH that wherein is used to deposit the fluid composition of the second layer is 7.0-8.5.

13. scribble the base material of the laminated coating of claim 1.

14. the base material of claim 13, wherein base material comprises polymeric substrate.

15. the base material of claim 14, wherein this polymeric substrate comprises the solid material of solid transparent or optically clear.

16. the base material of claim 15, wherein polymeric substrate comprises photochromic material.

17. the laminated coating of claim 1, wherein the second layer applies with the build of 20 to 60 nanometers.

18. the laminated coating of claim 1, wherein this base-material prepares by being selected from following technology:

(a) multistage process, it comprises: wherein react the phase I that forms the partial hydrolysis polycondensation product in the presence of the acid hydrolysis catalyst by organosilicon acid esters and water, wherein the amount of water is lower than the stoichiometric amount of organic group oxygen base that can this organosilicon acid esters of hydrolysis, wherein partial hydrolysis polycondensation product contact with a large amount of water the second stage that forms the organosilicon acid esters of hydrolysis fully basically and

(b) allow tetraalkoxysilane oligomer 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 group oxygen base that can this alkoxy silane of hydrolysis, to form the organosilicon acid esters of hydrolysis fully basically.

19. the laminated coating of claim 18, wherein this base-material prepares by multistage process.

20. the laminated coating of claim 19, wherein water exists with 50% stoichiometric amount of organic group oxygen base that can hydrolysis organosilicon acid esters in the phase I.

21. the laminated coating of claim 19, wherein the phase I carries out under the condition of restriction owing to the condensation degree of the formed Si-OH group of hydrolysis.

22. the laminated coating of claim 21, wherein restriction is owing to the condition of the condensation degree of the formed Si-OH group of hydrolysis is selected from by external refrigeration control exothermic heat of reaction, controls the interpolation speed of acid catalyst and/or carry out the phase I hydrolysis under the situation that does not have any organic cosolvent basically.

23. improve the soil resistance of goods, self-cleaning property, property easy to clean, and/or the method for anti-fogging performance, wherein these goods comprise the surface that deposits the coating that comprises inorganic oxide network, this method may further comprise the steps:

(1) at least a portion on surface, applies the fluid composition of the organosilicon acid esters that comprises basically hydrolysis fully; With

(2) be solidificated in the composition that applies in the step (1).

24. the method for claim 23, wherein step (2) is finished by the air drying.

25. the method for claim 23, the coating that wherein comprises inorganic oxide network comprises that network forms with the metal alkoxide thing.

26. the method for claim 25, wherein this network forms and comprises general formula R with the metal alkoxide thing _xSi (OR ') _4-xAlkoxy silane, wherein R is an organic group, R ' is that to be selected from the alkyl of methyl, ethyl, propyl group and butyl and x be integer and less than 4.

27. the method for claim 23, wherein the fluid composition that applies in step (1) further comprises catalysis material.

28. the method for claim 27, wherein catalysis material comprises the metal oxide that is selected from zinc oxide, tin oxide, iron oxide, bismuth oxide, tungstic acid, strontium titanates, titanium dioxide and their mixture.

29. the method for claim 27, wherein at least a portion of catalysis material exists with the particle form of the average crystal diameter of 3-35 nanometer.

30. the method for claim 27, wherein this catalysis material be selected from brookite type titanium dioxide, carry out titanium dioxide, plasma treatment titanium dioxide and their mixture that the titanium dioxide, nitrogen of chemical modification mix by flame pyrolysis.

31. the method for claim 27, wherein this catalysis material is present in the fluid composition that applies in step (1), based on the gross weight of composition with the amount of 0.1-0.75wt%.

32. the method for claim 23, wherein the organosilicon acid esters of the fluid composition that applies in step (1) is selected from organic group TMOS, organic group oxygen radical siloxane and their mixture.

33. the method for claim 23, wherein this organosilicon acid esters is to press SiO ₂The amount of meter 0.1-2wt% is present in the fluid composition that applies in step (1), based on the gross weight of composition.

34. the method for claim 23, wherein the pH of the fluid composition that applies in step (1) is no more than 3.5.

35. the method for claim 23, wherein the surface comprises the solid material of solid transparent or optically clear.

36. the method for claim 23, wherein the surface comprises photochromic material.

37. the method for claim 23, wherein the fluid composition that applies in step (1) applies with the build of 20-60 nanometer.

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