CN1926200A

CN1926200A - Surface-doped particles of TiO2 or ZnO and their use

Info

Publication number: CN1926200A
Application number: CN 200580006381
Authority: CN
Inventors: 加雷思·韦克菲尔德; 巴里·乔治·帕克; 萨拉·利普斯科姆; 爱德华·霍兰
Original assignee: Oxonica Ltd
Current assignee: Oxonica Ltd
Priority date: 2004-01-28
Filing date: 2005-01-26
Publication date: 2007-03-07
Also published as: GB0401846D0

Abstract

A particle of TiO2 or ZnO which has been doped with one or more other elements such that the concentration of dopant in the surface of the particle is greater than that at the core of the particle, and compositions containing such particles for use as sunscreens or in veterinary, agricultural or horticultural compositions or as coatings for plastics and other materials.

Description

The TiO of surface doping 2Or ZnO particle and application thereof

The present invention relates to new particle; this particle for example in being applicable to the UV barrier compositions of makeup and local medicinal application, in agricultural, gardening and veterinary purpose, and in machinery, building or environment protection, to find the having protectant effect of degraded such as the form of plastics, paint and varnish.

Britain at us applies in No. 0315082.8, also having zinc oxide or titanium dioxide and/or the reductive zinc oxide that is doped with other element in the composition if we have described, is how to delay organic opalizer and other degradation process to the responsive component of degrading.Unsettled shading becomes to assign to resist the photodegradation that sunlight causes to sunlight because it helps protection, so think that these materials are degraded protective materials.By using these adulterated or reductive material rather than common titanium dioxide or zinc oxide, it for example may provide than the composition that provides better UV photo-protection with organic opalizer of equivalent, perhaps has identical UV light shielding effect but contains the composition of organic opalizer of less amount.Really can provide the opalizer of all day protection effect by adding adulterated and/or reductive material.Sometimes degraded product (chemical substance of decomposition) is deleterious.

Though point out especially at this, can with from any characteristics combination in two or more these embodiments, but the present invention will be open with the form of four embodiments.First embodiment is paid close attention to particle itself; Second embodiment paid close attention to the composition that is used for makeup and local medicinal application, for example, and as the composition of UV opalizer; The 3rd embodiment paid close attention to and is used to provide machinery, composition building or environment protection; And the 4th embodiment concern is applicable to the composition animal doctor, agricultural or horticultural applications.

First embodiment

First embodiment of the present invention provides the TiO that mixes one or more other elements ₂Or the ZnO particle, make the concentration of hotchpotch in this particle surface greater than its concentration in this granular core.Used herein term " in the surface " means, and supposes a kind of globular particle that is essentially, and the thickness of its shell is no more than 10% of this particle radius.Should be appreciated that material existence is from the teeth outwards distinguished mutually under hotchpotch " in the surface " existence of (comprising " in the surface ") and the simple coating condition." in the surface " means hotchpotch is not to come in conjunction with described particulate by the pure electrostatic force under the coating condition.The term " core " used of place means since then, suppose a kind of globular particle that is essentially, the spheroid in this particle center, its radius be no more than this particle radius 10% (perhaps, in being essentially non-globular particle, its radius is no more than maximum sized 10%).Term " particulate main body " means the particle except that described shell.

The concentration of hotchpotch in described particle surface is preferably more than its concentration in this particulate main body, and undoped in this particulate core particularly preferably.In other words, exist concentration gradient, for example, make atoms of dopant in the surface to the ratio of titanium or zinc atom greater than its ratio at core or center, may be zero herein.

Can measure the optimal amts of second component on the described particle by normal experiment, enough low but total amount is preferably, thus the particle minimally is colored.Common spendable content is low to moderate 0.1% mol ratio or lower, 0.05% mol ratio for example, or high to 1% mol ratio or higher, for example 5% mol ratio or 10% mol ratio.Typical concentration is a 0.5-2 mole % weight ratio.From the teeth outwards, hotchpotch is generally 2-25 to the mol ratio of matrix metal: 98-75 is generally 5-20: 95-80, and especially be 8-15: 92-85.Hotchpotch content in the surface can be measured by for example sub-spectrography of X-ray photoelectric (XPS).

The hotchpotch that is applicable to described oxide particle comprise manganese (for especially preferred, Mn for example ²⁺But Mn especially ³⁺), vanadium (V for example ³⁺Or V ⁵⁺), chromium, cerium, selenium and iron, but spendable other metal comprises nickel, copper, tin (Sn for example ⁴⁺), aluminium, lead, silver, zirconium, zinc, cobalt (Co for example ²⁷), gallium, niobium (Nb for example ⁵⁺), antimony (Sb for example ³⁺), tantalum (Ta for example ⁵⁺), strontium, calcium, magnesium, barium, molybdenum (Mo for example ³⁺, Mo ⁵⁺Or Mo ⁶⁺) and silicon.These metals can add separately or add with 2 kinds or 3 kinds or more kinds of mixing.Should be appreciated that for effective main body and mix that ionic size must easily be inserted in the described particulate lattice.On the other hand, for the element that is used in the surface doping, there is not this size restriction; Preferred surface doping thing comprises manganese (Mn for example ²⁺), cerium, selenium, iron, chromium and vanadium.

Can obtain the particle of surface doping of the present invention by any standard method that is used to prepare this type of adulterated oxide compound and salt.Though can use other method that comprises flame pyrolysis when enough hotchpotchs being arranged, mix titanium dioxide and zinc oxide by two kinds of basic skills that relate to co-precipitation or absorption usually in the surface.Should be appreciated that co-precipitation causes hotchpotch distributing quite uniformly in whole particle usually, the result makes this method not be suitable for preparation described particle of the present invention usually.On the other hand, can easily use absorption process, be stopped this method as long as absorbed equably to core basically at described hotchpotch.In other words, if stop this method in certain stage, and should the stage early than the stage that is generally used for obtaining adulterated material, then can obtain the concentration of hotchpotch in the surface greater than particle in the concentration at core place.

This can reach by using for example short reaction times.Should be appreciated that described hotchpotch needn't be oxide compound, but may perhaps be salt for such as muriatic salt with oxo-anions such as perchlorate or nitrate.This technology comprises the technology of curing, by with parent lattice (TiO ₂/ ZnO) particle with at solution or suspension, be generally in the aqueous solution to mix such as muriatic salt or such as second component that the oxo-anions form of perchlorate or nitrate radical exists, it is cured being generally under at least 300 ℃ the temperature subsequently, then under higher temperature, for example under at least 500 or 600 ℃ with its calcining.Therefore, the invention provides and be used to prepare particulate method of the present invention, it comprises TiO ₂Or the ZnO particle contacts for some time with the solution or the suspension of the salt of described hotchpotch, and this deficiency of time cures resulting granules then so that the concentration of the salt of hotchpotch in this granular core reaches its concentration at this particle surface place.

Should be appreciated that, thisly cure the part that technology and similar techniques thereof will cause the hotchpotch formation lattice in the surface, and the hotchpotch in coating is retained on the particle surface as independent stratum.This just situation, if the doping material desire inner free radical that produces of cancellation effectively, it need be present in lattice so.

The photosensitivity of the rutile form of known titanium dioxide is not as anatase form, so preferred rutile form.

Zinc oxide through surface doping can be reductive zinc oxide.Can be at an easy rate by zinc oxide particle in reducing atmosphere to obtain reduction-oxidation zinc particle (promptly with respect to oxonium ion, particle with excessive zine ion), this reduction-oxidation zinc particle can absorb UV light, particularly wavelength is lower than the UV light of 390nm, lay equal stress on and launch green glow, be preferably about 500nm.Usually the concentration of hydrogen is about 1-20%, 5-15% volume ratio especially, and remaining gas is rare gas element, especially nitrogen.Preferred reducing atmosphere is the hydrogen of about 10% volume ratio and the nitrogen of about 90% volume ratio.Under this atmosphere, described zinc oxide such as about 500 °-1000 ℃, is generally 750-850 ℃, heating is 5-60 minute under for example about 800 ℃ temperature, is generally 10-30 minute.Usually be heated to 800 ℃, about 20 minutes.Preferred reducing gas is the hydrogen of volume ratio about 10% and about 90% nitrogen.Zinc oxide is heated in this gas, and for example 500 to 1000 ℃, be generally 750 to 850 ℃, for example 800 ℃, heated 5 to 60 minutes, be generally 10 to 30 minutes.Typically it was heated 20 minutes in 800 ℃.Be to be understood that the reductive Zinc oxide particles contains and the corresponding to reductive zinc oxide of minimum electronics that migrates to described particle surface and/or positive charge hole, therefore work as described particle as mentioned above and in aqueous environments, be exposed to the UV light time, significantly reduced the generation of hydroxyl radical free radical.

Believe that described reduction-oxidation zinc particle contains excessive Zn in the absorption core ²⁺Ion.These are localization (localised) attitudes, and this state can be present in the described band gap.Further argumentation to it is found in WO 99/60994.

Described particulate average primary particle size is generally about 1-200nm, for example about 1-150nm, preferably about 1-100nm, 1-50nm more preferably from about, and 20-50nm most preferably from about.Preferably granularity is selected to avoid final product color to occur.Therefore, often use nano particle.Owing to think that scavenging(action) is catalytic basically, therefore as far as possible little so that its surface-area maximization of advantageously described particle, and area maximization that therefore will be from the teeth outwards through dopant material.Small grain size has the following advantages: it needs the less doping thing, thereby has reduced any colour effect that is caused by this hotchpotch.Yet, in one embodiment, can use bigger slightly particle, for example about 100-500nm is generally 100nm to 400nm or 450nm, 150-300nm especially, and be in particular 200-250nm.These particles provide good opacifying property for the flaw on the skin for example, and do not cause unacceptable whiteness of skin.

When particle when being spherical substantially, then can use granularity to represent diameter.Yet the present invention also comprises aspheric particle, and described in this case granularity refers to maximum size.

Oxide particle used in this invention can have inorganic or organic coating.For example, this particle can be coated with the oxide compound such as aluminium, zirconium or element silicon, particularly silica or pure aluminium silicate for example.Metal oxide particle also can be coated with one or more organic materialss, such as polyvalent alcohol, amine, alkanolamine, poly organic silicon compound, and RSi[{OSi (Me) for example ₂} _xOR ¹] ₃, wherein R is C ₁-C ₁₀Alkyl, R ¹For methyl or ethyl and x are the integer of 4-12, hydrophilic polymer, such as polyacrylamide, polyacrylic acid carboxymethyl cellulose and xanthan gum, or tensio-active agent, for example TOPO.If desired, surface doping can combine individually or with the organic or inorganic coating-forming agent by coating technology and carry out.Therefore, for example unadulterated oxide compound can be such as being coated with manganese oxide together with organic or such as the inorganic coating agent of silica.Usually, need not to apply oxide particle so that it is hydrophilic, therefore, for water, this particle can not have coating.But if this particle will place organic or oil phase, their surface needs hydrophobic property or oil-dispersing property.This can realize by for example suitable hydrophobic polymer of direct coating, or indirectly by applying for example oxide coating of silica (it gives hydrophilicity), is hydrophobic molecule then, for example metallic soap or long-chain (C for example ₁₂-C ₂₂) carboxylic acid or its metal-salt, realize such as stearic acid, stearate, particularly aluminum stearate, Aluminum trilaurate and Zinic stearas.

It should be understood that term " coating " is not to be construed as being limited to whole coverings.In fact, because coating can be used as on free radical and the particle surface or the interactional obstacle of interior hotchpotch, useful is incomplete coating usually.Therefore, when the scavenging(action) of hope maximum, preferably this coating should be discontinuous.What however, it should be understood that is, lip-deep hotchpotch still can play the free radical that produces in the cancellation particle, in this case, coating can the time successive.Because the silane and the silicon coating that can be polymerization or short chain or monomeric silanes are generally successive, not too preferred usually they.Therefore, owing to have the coating fully that the coating of inorganic oxide does not cause particle surface usually, common preferred this coating.

Typical coating method comprises by mixing the deposition of carrying out silica with orthosilicate such as tetraethyl orthosilicate salt when this particle exists such as the alkali of ammonium hydroxide.Perhaps, this particle can at first be coated with the silane such as (3-sulfydryl propyl group) Trimethoxy silane (MPS), adds the silicate such as water glass then.Also as the substrate of silicate, then the silicate polymerization forms silica to silane attaches to particle surface.Similar techniques can be used for other inorganic oxide.

Particle of the present invention can be used for all compositions that we describe in the UK Patent Application of pending trial simultaneously referred to above, and another polymkeric substance and Pestcidal compositions described in the UK Patent Application of pending trial simultaneously that also be used for us, this application and the application are in submission on the same day, and title is Improved Polymeric Composition and ImprovedAgricultural Compositions (improved polymeric composition and improved Pestcidal compositions).

Following examples have further exemplarily been described the present invention.

Embodiment 1

The titanium dioxide of acid extraction doped with manganese

At room temperature, the titanium dioxide sample of doped with manganese is flooded different time in 25% hydrochloric acid.Precipitate this titanium dioxide by centrifuging, supernatant liquor is transferred in the volumetric flask of 50ml.By by means of ultrasonic wave, this titanium dioxide is suspended in the water carrying out once washing again, and recentrifuge.Washes is added in this volumetric flask, and make its capacity reach 50ml with deionized water.

With the sample of extract, together carry out analysis to manganese with initial powdered sample.By AAS (atomic absorption spectrometry) direct analysis water extract.After with hydrofluoric acid-sulfuric acid mixture digestion, this powder is similarly analyzed.

DPPH (free radical scavenging) analyzes

The storing solution of preparation 1mM DPPH in MeOH.The DPPH (1mM) and the 300 μ l TiO that will contain 120 μ l with MeOH ₂Specimen preparation (3mg/ml) becomes 3ml, and places the 10mm quartz curette.Therefore DPPH is stable free radical, and it is absorbed in 520nm, and the loss in the light absorption ratio of this wavelength is to measure TiO ₂Remove the method for free radical ability.From the extract of above-mentioned series, obtain titanium dioxide sample.This sample is placed dark, and the light absorption ratio of measuring at 520nm in per 5 minutes.In order to disperse TiO ₂, need to mix this sample before each the measurement.

Time shutter (hour)	The Mn (%) of extraction	The loss speed of DPPH (mAbs/ minute)
Time shutter (hour)	The Mn (%) of extraction	The loss speed of DPPH (mAbs/ minute)	0	0	3.4
0.25	3.22	2.05	0	0	3.4
0.25	3.22	2.05	1.5	4.58	1.6
48	26.0	0.35	1.5	4.58	1.6

From these data, it is evident that and after 48 hours, remained 74% manganese.Therefore obviously because the rate of loss of DPPH is very little, remaining manganese of 26% has played the removing free radical in the surface or on the surface.Therefore the particle that contains available manganese in the surface will be removed free radical.

Second embodiment

Second embodiment of the present invention relates to the degraded protective material in being applicable to the UV sunscreen composition of makeup and local medicinal application.

Skin is exposed to that caused consequence is well-known under UVA and the UVB light, and it comprises, for example, sunburn, crosses presenility and skin carcinoma.

Commercial opalizer contains the component that can reflect and/or absorb UV light usually.These components comprise, for example, and such as inorganic oxide and organic opalizer of zinc oxide and titanium dioxide.

Compare with other the distant consequence that is caused by sunlight, the public more pays close attention to the remarkable consequence of sunlight usually, promptly causes the sunburn of skin rubefaction.Therefore, evaluate the commercial sunscreen composition of this class with sun protection factor (SPF).This method is to compare with undressed skin, measures the required time of erythrosis that is coated with a layer composition.Therefore SPF20 represents to compare with undressed skin, with 2mg/cm ²The skin that is coated with a layer composition needs 20 times longer time just can redden.The result who reddens is mainly caused by UVB light.Effect for UVA light does not also have generally acknowledged corresponding factor, even the latter has more nocuity on long terms.

Most of organic opalizers only absorb a part of light in the UVA-UVB wave spectrum, consequently, cover whole UVA-UVB spectrographic shaded effects if seek out, and need to use the combination of different organic opalizers usually.Other component in some organic opalizers and the sunscreen composition is only stable to UV, and other component is photosensitive and/or the formation that can be caused free radical after the UV optical excitation, and the degraded of other composition in the said composition is attacked and caused to this free radical.

Because according to Rayleigh ' s law; granularity is less than 10% particle scattered beam of lambda1-wavelength; and the biquadratic of scattered intensity and wavelength is inversely proportional to, and therefore usually titanium dioxide and zinc oxide is formulated as " micronized " or " superfine " (20-50nm) particle (so-called little reverberation).As a result, compare with the visible light that wavelength is longer, it is scattering UVB light (wavelength is from the wavelength of 280nm or 290nm to 315/320nm) and UVA light (wavelength is from 315/320nm to 400nm) more, thereby prevent sunburn, keeps invisible simultaneously on skin.

Yet carbonic acid gas and zinc oxide also absorb UV light effectively, and the electron-hole pair by initial formation forms super-oxide and hydroxyl radical free radical when causing contacting with water, itself so that may cause damage to other composition of described composition.TiO ₂Anatase octahedrite and rutile crystal form all be semi-conductor, have 3.23 and the band-gap energy of 3.06eV respectively, (1eV is equivalent to 8066cm corresponding to the light of about 385nm and 400nm ^-1).In fact, evidence shows TiO ₂Can strengthen and comprise the organic opalizer of UVA, for example the Degradation of organic opalizer of avobenzone (butyl methoxyl group DBM is also referred to as BMDM).Once attempted reducing TiO by coating ₂With the detrimental action of ZnO, but coating is not constant effective.

The reason that most of opalizers do not have dauer effect (be the SPF factor keeps substantially constant) basically mainly is because organic opalizer is degraded by light, in case and/or other component of sunscreen composition contact UV light time, it is subjected to the detrimental action of this other component.

Therefore, the present invention also provides and has reduced the method that toxic compounds produces in the UV sunscreen composition, and it comprises to wherein adding adulterated TiO ₂/ ZnO and/or reductive ZnO.With except that do not contain have same recipe the adulterated material composition compare, contain adulterated TiO usually ₂The UV absorption loss rate of the composition of/ZnO is low at least by 5%, is preferably lowly by at least 10%, more preferably low at least by 15%, low especially at least by 20%, and most preferably is at least low 40%.Therefore, if the UV absorption loss rate (during being exposed to UV) in described UVA of at least a portion and/or UVB spectrum is X, then the described absorption loss rate that has of the measurer of the organic constituent of the degraded of other composition in the photosensitive and/or the thing that is combined is Y, and wherein Y is bigger at least by 5% than X, adulterated TiO ₂And/or the amount of ZnO is reduced to X with described rate of loss by Y.

Should be appreciated that now that according to the present invention key is if desire to make described oxide compound really effective, then in its surface must existence can with the hotchpotch of the component interaction of desire protection in the described composition.For example, if in two-phase compositions, described oxide compound is present in water, and the described component of desire protection is present in organic phase, so then because phase boundary seldom has interaction; Not accessible this component of this oxide compound.Therefore, the free radical that is produced by the Degradation of this component then can not contact described hotchpotch from a phase shift to another phase time.It is also to be understood that if described hotchpotch exists only in the main body, then its can not (as free-radical scavengers) effectively with described composition in the component interaction of desire protection.Only consequently may use material, promptly wherein in described particulate surface or have hotchpotch on the surface at surface doping.In one embodiment, this material can be used in the monophasic preparation.Though body dopants is fit to when described combination material desire protection skin, because free radical that the effect by UV light of can catching of this hotchpotch produces and the energy that dissipates and produce, it is unnecessary for the preparation of not planning to have the skin care effect.Should remark additionally, opposite with the surface doping thing, body dopants is had an effect residing irrelevant mutually with described particle.

Therefore, the invention provides the UV sunscreen composition (although not relying on above-mentioned theory) that is applicable to that makeup or part drug use, it comprises: (a) one or more photosensitive and/or be easy to by other composition of said composition and/or by unadulterated TiO ₂And/or the organic constituent of being degraded by unadulterated ZnO; And (b) surface doping has one or more TiO ₂/ ZnO, this other element is generally a kind of, i.e. second element.When described particle is mixed by main body, then in whole particle, there is hotchpotch usually.On the other hand, when described particle quilt " surface doping " (being that described hotchpotch is only in the surface or on the surface), then there is concentration gradient, for example, so that atoms of dopant to titanium or zinc atom ratio that this particle surface place or outermost " skin " are located greater than core or in intracardiac ratio, may be zero here.

" the UV sunscreen composition that is suitable for makeup or part drug's purposes " is meant any makeup with UV sunscreen activity or local medicine composition, and promptly it comprises that major function can not be the composition of shading.Should be appreciated that described adulterated TiO ₂/ ZnO or reductive ZnO can be the unique components that has the UV sunscreen activity in the composition, and promptly said composition might not contain organic UV opalizer.Should be appreciated that described composition also can contain not doping or unreduced TiO ₂And/or ZnO.

Photosensitive or by the organic constituent of other component degradation in described composition UV opalizer normally.Though can use all organic opalizers that incur loss when UV absorbs, the present invention is to particularly useful at the reagent of UVA district and the absorption of UVB district.But other organic constituent is subject to the attack of free radical usually, thereby can cause the degraded of described UV opalizer usually.

As mentioned above, the UV of organic opalizer absorbs and reduces in time usually.On the contrary, TiO ₂Or the UV of ZnO absorption does not reduce in time.Because TiO ₂At UVA and UVB district absorption is arranged all with ZnO, and organic opalizer has more wavelength specific usually, so but can see UVA/UVB assimilation ratio time to time change.For example, preferably, when described organic opalizer absorbed in the UVA district, then this ratio reduced in time.When using adulterated TiO ₂/ ZnO, rather than the unadulterated TiO of use equal amts ₂During/ZnO, then rate of change reduces.This is because with respect to there being unadulterated TiO ₂Under the situation of/ZnO, adulterated material can strengthen the performance of organic opalizer in time.Therefore, for the UVA opalizer, the loss that UVA absorbs in time is reduced (promptly the UVA reaction is more stable when described adulterated material exists), so the speed that ratio changes reduces.Therefore, if the initial absorption ratio is X/Y, then when using adulterated material, it becomes (X-x)/Y, and wherein x is littler, and consequently rate of change is less.For the UVB opalizer, because more stable UVB reaction, so rate of change also reduces.

Apply for described in No. 0315082.8 as Britain, can be by with UV light containing and not containing described adulterated TiO to specific thickness ₂And/or the composition sample of ZnO is shone mensuration absorption loss rate.

Though should be understood that generally body dopants and surface doping thing are identity element (for simplifying preparation), this might not be necessary situation (certainly, for reductive zinc oxide, not having body dopants).For example may change described particulate color in this way.The hotchpotch that is applicable to described oxide particle comprise manganese (especially preferred, Mn for example ²⁺And Mn ⁴⁺But more preferably Mn ³⁺), vanadium (V for example ³⁺Or V ⁵⁺), chromium and iron, but spendable other metal comprises nickel, copper, tin, aluminium, lead, silver, zirconium, zinc, cobalt, gallium, niobium (Nb for example ⁵⁺), antimony (Sb for example ³⁺), tantalum (Ta for example ⁵⁺), strontium, calcium, magnesium, barium, molybdenum (Mo for example ³⁺, Mo ⁵⁺Or Mo ⁶⁺) and silicon.Manganese is preferably with Mn ³⁺Form exists, and cobalt is preferably Co ²⁺, tin is preferably Sn ⁴⁺And preferred manganese is Mn ²⁺These metals can add separately or can 2 kinds or 3 kinds or more kinds of mixing adding.Should be appreciated that for effective main body and mix that ionic size must easily be inserted in the described particulate lattice.For this reason, Mn ³⁺, vanadium, chromium and iron is normally the most effective; Mn ²⁺Ionic size compare Ti ⁴⁺Ionic size bigger, therefore Mn is seldom arranged ²⁺Ion diffusion enters TiO ₂Intracell possibility.On the other hand, for the element that is used for surface doping, there is not this size restriction; Preferred surface doping thing comprises manganese (Mn for example ²⁺), cerium, selenium, chromium and iron and vanadium, be generally V ⁴⁺

Can determine on the described particle and the optimal amts of second component of (if exist) in the particle by normal experiment, enough low but total amount is preferably, thus the particle minimally is colored.Common spendable content is low to moderate 0.1% mol ratio or lower, 0.05% mol ratio for example, or high to 1% mol ratio or higher, for example 5% mol ratio or 10% mol ratio.Typical concentration is a 0.5-2 mole % weight ratio.From the teeth outwards, hotchpotch is generally 2-25 to the mol ratio of matrix metal: 98-75 is generally 5-20: 95-80, and especially be 8-15: 92-85.Hotchpotch content in the surface can be measured by for example sub-spectrography of X-ray photoelectric (XPS).

Can obtain the particle of described surface doping by any standard method that is used to prepare this type of adulterated oxide compound and salt.This comprises technology as described below.Should be appreciated that described hotchpotch not necessarily must exist with oxide form, but may be to exist such as muriatic salt or such as the salt form with oxo-anions of perchlorate or nitrate.But the main body doping techniques also causes some surface dopings usually, and these technology can be used for the present invention.This class technology comprises the technology of curing, by with parent lattice (TiO ₂/ ZnO) particle with at solution or suspension, be generally in the aqueous solution to mix such as muriatic salt or such as second component that the oxo-anions form of perchlorate or nitrate radical exists, it is cured being generally under at least 300 ℃ the temperature subsequently.Can be used for preparing described other approach and comprise J.Mat.Sci. (1997) 36 through adulterated material, the intermediate processing of type described in the 6001-6008, wherein the solution with the salt of hotchpotch mixes with the solution of the alkoxide of matrix metal (Ti/Zn), makes this alkoxide be converted into oxide compound the heating of gained mixing solutions subsequently.Continue heating till the precipitation that obtains adulterated material.Preparation method's more details are referring to WO 00/60994 and WO 01/40114.

Should be appreciated that and thisly cure the part that technology and similar techniques thereof will cause the hotchpotch formation lattice in the surface, and in other technology, described hotchpotch only is adsorbed or is retained on the described particle surface as independent stratum.This just situation, if the doping material desire inner free radical that produces of cancellation effectively, it need be present in the lattice so.

Can obtain adulterated TiO by flame pyrolysis or plasma body approach ₂Or adulterated ZnO, wherein will be exposed in flame or the plasma body, to obtain required product with the hybrid metal that suitable dopant levels contains precursor.

Through the zinc oxide of surface doping can be reductive zinc oxide when inspection of skin provide protection (current).Can be at an easy rate by zinc oxide particle in reducing atmosphere, to obtain reduction-oxidation zinc particle (promptly with respect to oxonium ion, particle with excessive zine ion), this reduction-oxidation zinc particle can absorb UV light, particularly wavelength is lower than the UV light of 390nm, lay equal stress on and launch green glow, be preferably about 500nm.Usually the concentration of hydrogen is about 1-20%, 5-15% volume ratio especially, and remaining gas is rare gas element, especially nitrogen.Preferred reducing atmosphere is the hydrogen of about 10% volume ratio and the nitrogen of about 90% volume ratio.Under this atmosphere, described zinc oxide such as about 500 °-1000 ℃, is generally 750-850 ℃, heating is 5-60 minute under for example about 800 ℃ temperature, is generally 10-30 minute.Usually be heated to 800 ℃, about 20 minutes.Be to be understood that the reductive Zinc oxide particles contains and the corresponding to reductive zinc oxide of minimum electronics that migrates to described particle surface and/or positive charge hole, therefore work as described particle as mentioned above and in aqueous environments, be exposed to the UV light time, significantly reduced the generation of hydroxyl radical free radical.

Believe that described reduction-oxidation zinc particle contains excessive Zn in the absorption core ²⁺Ion.These are localized states, and this state can be present in the described band gap.To the visible WO 99/60994 of its further argumentation.

It should be understood that term " coating " is not to be construed as being limited to whole coverings.In fact, because coating can be used as on free radical and the particle surface or the interactional obstacle of interior hotchpotch, useful is incomplete coating usually.Therefore, when the scavenging(action) of hope maximum, preferably this coating should be discontinuous.What however, it should be understood that is, lip-deep hotchpotch still can play the free radical that produces in the cancellation particle, and in this case, coating can be a successive.Because the silane and the silicon coating that can be polymerization or short chain or monomeric silanes are generally successive, not too preferred usually they.Therefore, owing to have the coating fully that the coating of inorganic oxide does not cause particle surface usually, common preferred this coating.

Typical coating method comprises by mixing the deposition of carrying out silica with orthosilicate such as tetraethyl orthosilicate salt when this particle exists such as the alkali of ammonium hydroxide.Perhaps, this particle can at first be coated with the silane such as (3-sulfydryl propyl group) Trimethoxy silane (MPS), adds the silicate such as water glass then.Also as the substrate of silicate, then the silicate polymerization forms silica to silane attaches to particle surface.Preferably, extract described material,, thereby make described particle keep less because this sublimating technologe reduces the formation of hydrogen bond by lyophilize.Typical working method is as follows:

A) 4.52g titanium dioxide is added in the 200ml deionized water.Ultrasonic horn is used to disperse described material.

B) under vigorous stirring, 1.89ml (3-sulfydryl propyl group) Trimethoxy silane [MPS] is added in the 50ml water.

C) under vigorous stirring, 20ml MPS solution is added in the titania solution.With this solution stirring 2 hours, make MPS be attached to the surface.

D) 25% sodium silicate solution of adding 40ml, and stirred solution 1 hour.Silica is deposited on the MPS layer lentamente.

E) titanium dioxide is removed by centrifuging, and washs three times in deionized water.

F) with the material lyophilize.Thereby the silica layer that a little nm is thick is coated on titanium dioxide surface.

Similar technology can be used for other inorganic oxide.

Composition of the present invention can be single-phase for water-based or butyrous, perhaps is heterogeneous.Typical two-phase compositions is oil-in-water-type or water-in-oil-type preparation.For single-phase composite, oxide particle should be dispersed in certainly this mutually in.Therefore, be hydrophilic if composition is this particle of hope of water-based, if composition is based on oil, wish that then this particle is hydrophobic.But may be with untreated TiO by suitable hybrid technology ₂Be dispersed in the oil phase.For two-phase or multiphase composition, this particle should be present in contain the composition that will protect one of (or composition) mutually in.Be present in water and the oil phase but it is desirable to this particle, even there is not the composition that will protect in these one in mutually in mutually.This can include that the user uses said composition and situation during certain phase transition of the composition that causes protecting.Also have, when emulsion is coated on the skin, it trends towards being decomposed into oiliness district and non-oiliness district.When water evaporates, oily dispersible granules will be tending towards staying not protection zone thus in the oiliness zone.Can have hydrophilic and hydrophobic granule in the emulsion by making, so that some are retained in the hydrophilic region, other are retained in the hydrophobic region, prevent above-mentioned situation.But but the weight ratio of wishing water discrete particles and oil discrete particles is 1: 4 to 4: 1, and preferred 1: 2 to 2: 1, ideal was the equivalent ratio.A lot of organic opalizers are hydrophobic, so this particle should be hydrophobic, but some organic opalizers that especially rely on acidic group are water miscible, and at this moment this particle need be for hydrophilic so that protect them.

Composition of the present invention is generally used for cosmetic use; for example can be for example skin tanning composition of paste form; lipstick; the skin anti-aging composition of paste form for example; comprise wrinkle-resisting preparations; skin preparation agent comprises sanitising agent; paste and lotion; the cosmetic composition of face cream form for example; the preparation that is used for hand that comprises cream and lotion; wetting Agent for Printing Inks; be used to protect the composition of hair; as conditioning agent; shampoo; hair jelly (hair lacquer) and film and gelifying agent; skin cleansing compositions comprises liniment; lotion and gelifying agent; eye shadow and kermes; skin contraction agent and slurries and cleaning product; such as shower gels, bath article comprises bubble bath; bathe oil, but preferred opalizer.About this point, we should point out that " cosmetic UV sunscreen composition " used herein statement comprises any skin can stay resistates on skin composition that is administered to, as some articless for washing.Composition of the present invention can use as any common dosage forms of UV light protection that provides.Said composition also can be and is suitable for pharmaceutical composition for topical application.This based composition especially is of value to suffers from dermopathic patient, and UV light has undesirable action to this tetter, as polymorphous light eruption.

Can be used on organic opalizer in the present composition and comprise any opalizer that the protection of UV light is provided commonly used, if there is not other photosensitive component, this opalizer be photosensitivity and/or by another composition degraded in the said composition.The opalizer that is fit to is listed in the IARC Handbook of Cancer Prevention that published calendar year 2001 by the international office (International Agency for Research on Cancer) of Lyons cancer research (IARC give protection against cancer handbook), vol.5, among the Sunscreens (opalizer), comprising:

(a) para-amino benzoic acid (PABA), (UVB absorption agent), its ester and its derivative, for example the amyl group dimethyl-; The ethyl dihydroxypropyl-; The ethylhexyl dimethyl-; Ethyl-; Glyceryl-; And 4-couple-(polyethoxye)-PABA.

(b) styracin (UVB), especially ester, comprise tolyl acrylic acid ester and Methoxycinnamate, for example octyl methoxycinnamate, methoxy cinnamic acid ethyl ester, especially 2-ethylhexyl p-methoxycinnamic acid ester, isopentyl p-methoxycinnamic acid ester, and they and di-isopropyl cinnamate, 2-ethoxyethyl group-4-methoxy cinnamic acid salt, DEA-methoxy cinnamic acid salt (to the diethanolamine salt of methoxyl group-hydroxycinnamic acid) or α, β-two-(to the methoxyl group cinnyl)-α '-(2-ethyl hexanoyl)-glycerine and di-isopropyl tolyl acrylic acid ester;

(c) benzophenone (UVA), for example 2, the 4-dihydroxyl-; 2-hydroxyl-4-methoxyl group; 2,2 '-dihydroxyl-4,4 '-dimethoxy-; 2,2 '-dihydroxyl-4-methoxyl group-; 2,2 ', 4,4 '-tetrahydroxy-; With 2-hydroxyl-4-methoxyl group-4 '-methyl-benzophenone, Phenylsulfonic acid and its sodium salt; 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-diphenylsulfone ketone sodium and oxybenzone

(d) diphenylpropane-1,3-dione(DPPO) (UVA), for example butyl methoxydibenzoylmethise, particularly the 4-tertiary butyl-4 '-methoxy dibenzoyl methane;

(e) 2-Phenylbenzimidazole base-5 sulfonic acid UVB and phenyl bisbenzimidazole base sulfonic acid and their salt;

(f) alkyl-β, β-diphenylacrylate (UVB), for example, and alkyl alpha-cyano-β, β-diphenylacrylate ester is as Viosorb 930;

(g) triazine (UVB), such as 2,4,6-triphen amido-(right-carbonyl-2-ethyl-hexyl-1-oxygen base)-1,3,5 triazines and UVINUL T-150, for example ethylhexyl triazone and diethylhexyl butyramide triazone.

(h) camphor derivatives (UVB usually), such as 4-methyl benzylidene and 3-benzylidene camphor (UVA) and Terephthalidene Dicamphor Sulfonic Acid (UVA), benzylidene camphor sulfonic acid, camphor benzalkonium methosulphate and polyacrylamide base methyl benzylidene camphor;

(i) organic pigment opalizer, for example methylene-bis benzotriazole tetramethyl butyl phenol;

(j) based on the opalizer of silicone, such as dimethicodiethyl Ben Yajiaji propanedioic acid.

(k) salicylate (UVB), such as the dipropylidene diol base-; Ethylene glycol-, ethylhexyl-, isopropyl benzyl-, methyl, phenyl, 3,3,5-trimethylammonium and TEA-Whitfield's ointment (2 hydroxybenzoic acid and 2,2 ', 2 "-nitrilo three (ethanol) compound);

(l) cinnamyl o-aminobenzoate (UVA), for example anthranilic acid ester in the Meng, and bisymidazylate (UVA), dialkyl group trioleate (UVB), 5-methyl-2-Ben base benzoxazole (UVB) and urocanic acid (UVB).

Some compounds are all effective to UVA and UVB.These comprise methylene-bis benzotriazole base tetramethyl butyl-phenol and drometrizole trisiloxanes (Mexoryl XL).

Based on the weight of composition, organic by weight opalizer typically is present in the composition with the concentration of 0.1-20%, preferred 1-10%, particularly 2-5%.

In composition, metal oxide preferably is the concentration of about 0.5-20% weight ratio, the concentration of preferably about 1-10% weight ratio mutually or in heterogeneous in one of its existence, the concentration of 3-8% weight ratio more preferably from about, especially about 4-7%, such as 4-6%, for example about 5% weight ratio.

This based composition for example form of lotion exists, typically has 4000-10, the viscosity of 000mPas, for example lotion of thickening, gelifying agent, vesica dispersion, paste, 10,000-20, the typical liquid paste of the viscosity of 000mPas, or viscosity 20,000-100, the paste of 000mPas, milk, powder, solid bar, and can randomly be packaged as aerosol and provide with the form of foam or jetting fluid.

Said composition can contain any composition that is used in this class preparation, comprise fatty substance, organic solvent, silicone, thickening material, liquid and solid softener, negative catalyst, other UVA, UVB or wide band opalizer, defoamer, antioxidant such as butylhydroxy toluene, contain buffer reagent such as lactic acid such as trolamine or sodium hydroxide, such as aloe vera (Aloe vera), Minor centaury, witch hazel, the plant milk extract of sambucus and cucumber, active reinforcing agent, moistening agent and wetting agent such as glycerine, sorbyl alcohol, 2-Pyrrolidone-5-carboxylate salt, DBP, gelatin and polyoxyethylene glycol, spices, sanitas, p-Hydroxybenzoate for example, tensio-active agent, weighting agent and thickening material, sequestrant, negatively charged ion, positively charged ion, nonionic or amphiphilic polymers or their mixture, propelling agent, basifier or souring agent, tinting material and powder, the metal oxide pigment that comprises particle diameter 100nm-20000nm, for example TiO of ferriferous oxide and (undoped) commonly used ₂And ZnO.

Known other the make-up composition composition of for example some tensio-active agents can have the effect of some opalizer of degraded under UV light.Also known, TiO ₂With ZnO some organic opalizer of degrading, for example avobenzone and antioxidant are such as VITAMIN, as vitamin A, B, C and E.Be understood that and adopt the TiO that mixes ₂And/or ZnO and or reductive ZnO be useful especially with this class opalizer.This is because TiO ₂Generally has male UV sorption with ZnO.Therefore, the TiO that mixes when employing ₂And/or ZnO and or reductive ZnO, may adopt antioxidant still less or make said preparation more durable.

Organic solvent generally includes lower alcohol and polyvalent alcohol, such as ethanol, Virahol, propylene glycol, glycerine and sorbyl alcohol and methylene dichloride, acetone, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ether, methyl-sulphoxide, dimethyl formamide and tetrahydrofuran (THF).

Fatty substance can comprise oil or wax or its mixture, lipid acid, fatty acid ester, Fatty Alcohol(C12-C14 and C12-C18), Vaseline, paraffinic hydrocarbons, lanolin, hydrogenated lanolin, Modulan, beeswax, ceresine and paraffin.

Oil typically comprises animal, plant, mineral or synthetic oil, particularly hydrogenated palm kernel oil, hydrogenated castor oil, vaseline oil, paraffin oil, purcellin oil, silicone oil such as polydimethylsiloxane and isoparaffin.

Wax typically comprises animal, fossil, plant, mineral or synthetic wax.This class wax comprises beeswax, carnauba wax, the wax root of Beijing euphorbia, sugarcane or Japan tallow, ceresine, montanin wax, Microcrystalline Wax, paraffin or silicone wax and resin.

Fatty acid ester for example is Isopropyl myristate, hexanodioic acid isopropyl ester, Wickenol 111, Wickenol 155, C ₁₂-C ₁₅Fatty Alcohol(C12-C14 and C12-C18) benzoic ether (from " FINSOLVIN " of FINETEX), the propylene oxide Semen Myristicae acid alcohol (from " the WITCONOL APM " of WITCO) that contains 3 mole propylene oxide, capric acid and Trivent OCG (from " MIGLYOL 812 " of HULS).

Said composition also can contain thickening material, such as crosslinked or noncrosslinking acrylate copolymer, particularly adopt the crosslinked polyacrylic acid of poly functional reagent, for example GOODRICH company is with " CARBOPOL " trade(brand)name product sold, the derivative of the sodium salt of Mierocrystalline cellulose, for example methylcellulose gum, Walocel MT 20.000PV, Vltra tears, carboxymethyl cellulose, 16 stearyl alcohol and ethylene oxideization 16 stearyl alcohol that contain 33 mole ethylene oxides.

The negative catalyst that is fit to comprises stearyl alcohol; single ricinoleic acid glyceryl ester; spearmint oil; ermine oil; hexadecanol; the Unimac 5680 isopropyl ester; stearic acid; the palmitinic acid isobutyl ester; Standamul 7061; oleyl alcohol; isopropyl laurate; lauric acid hexyl ester; decyl oleate; octadecane-2-alcohol; different hexadecanol; eicosanol; behenyl alcohol; cetin; silicone oil such as dimethyl polysiloxane; n-butyl sebacate; Isopropyl myristate; Wickenol 111; isopropyl stearate; butyl stearate; polyoxyethylene glycol; triglycol; lanolin; theobroma oil; Semen Maydis oil; Oleum Gossypii semen; sweet oil; palm-kernel oil; rapeseed oil; safflower oil; evening primrose oil; soybean oil; sunflower seed oil; Lipoval A; sesame oil; Oleum Cocois; peanut oil; Viscotrol C; Acetylated lanolin alcohols; vaseline; mineral oil; butyl myristate; Unimac 5680; palmitinic acid; the linolic acid isopropyl ester; Lauryl lactate; Tetradecyl lactate; decyl oleate; Tetradecyl tetradecanoate.

The propelling agent that is fit to comprises propane, butane, Trimethylmethane, dme, carbonic acid gas, nitrous oxide.

The powder that is fit to comprises neusilin, the polynite of organic decoration, hydrated aluminium silicate, fumed silica, carboxy vinyl polymer, Xylo-Mucine, the Tego-stearate of chalk, talcum, Fuller's earth, kaolin, starch, vegetable jelly, polyacrylic acid colloidal silica sodium, tetraalkyl and/or trialkyl aryl montmorillonite, chemically modified.

When composition of the present invention is opalizer, they can for example be suspension or dispersion in solvent or the fatty substance, or the form of the emulsion of conduct such as paste or milk sap, can be ointment, gel, solid bar (solid stick) or aerosol foam form.Emulsion can be oil-in-water-type or water-in-oil emulsion, and it also can contain emulsifying agent, and this emulsifying agent comprises negatively charged ion, nonionic, positively charged ion or zwitterionics; For water-in-oil emulsion, HLB typically is 1-6, and bigger value promptly＞6 is that oil-in-water emulsion is desirable.Usually, water content by volume as many as 80% typically is 5-80%.Adoptable specific emulsion comprises three oleic acid sorbitan esters, three stearic acid sorb glycan esters, XU 61518.10, glyceryl monostearate, glyceryl monolaurate, sesquialter oleic acid sorbitan ester, single oleic acid sorbitan ester, the Stearinsaeure sorbitan ester, polyoxyethylene (2) stearyl ether, polyoxyethylene Sorbitol Powder beeswax derivative, PEG 200 dilaurates, single palmitinic acid sorbitan ester, polyoxyethylene (3.5) nonylphenol, PEG 200 monostearates, the Stearinsaeure sorbitan ester, the mono laurate sorbitan ester, PEG 400 dioleates, polyoxyethylene (5) mono-laurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (4) bay ether, polyoxyethylene (5) sorbitanic monoleate, PEG 300 monoleates, polyoxyethylene (20) sorbitanic tristearate, polyoxyethylene (20) sorbitanic trioleate, polyoxyethylene (8) monostearate, the PEG400 monoleate, PEG 400 monostearates, polyoxyethylene (10) monoleate, polyoxyethylene (10) stearyl ether, polyoxyethylene (10) cetyl ether, polyoxyethylene (9.3) octyl phenol, polyoxyethylene (4) sorbitanic mono-laurate, PEG 600 monoleates, PEG 1000 dilaurates, polyoxyethylene Sorbitol Powder lanolin derivative, polyoxyethylene (12) bay ether, PEG 1500 dioleates, polyoxyethylene (14) laurate, polyoxyethylene (20) gathers the Sorbitol Powder monostearate, polyoxyethylene (20) gathers sorbitol monooleate, polyoxyethylene (20) stearyl ether, polyoxyethylene (20) gathers the Sorbitol Powder monopalmitate, polyoxyethylene (20) Sorbitol Powder cetyl ether, polyoxyethylene (25) propylene oxide monostearate, polyoxyethylene (20) is sorbityl monododecanoate, polyoxyethylene (23) bay ether, polyoxyethylene (50) monostearate and PEG 4000 monostearates.Perhaps, this emulsifying agent can be silicone surfactant, especially has the dimethyl polysiloxane of polyoxyethylene and/or polyoxytrimethylene side chain, typically have 10,000-50, the polyvalent alcohol of 000 molecular weight, especially cyclopolymethyl siloxane and polydimethylsiloxane.The vesica dispersion form of ion that they also can prepare in accordance with known methods or nonionic amphoteric lipid provides.

The embodiment 1 that provides in above-mentioned first embodiment, following examples are also exemplarily described embodiment of the present invention.

Embodiment 2

Between the preparation that only adds TiO2 of different nature, compare.

The preparation of opalizer preparation

Described opalizer preparation is based on Stanley Black method (www.sblack.comFormula Reference 1629).

The A phase

％w/w

Water 80.35

Propylene glycol 2.00

Methyl p-hydroxybenzoate 0.15

Aloe vera gel (Aloe Vera Gel) x1 0.10

The B phase

Lexemul 561 (stearin, 5.00

The PEG-100 stearate)

Lexemul GDL (GLYCERYL DILAURATE) 1.50

Stearyl alcohol NF 0.30

Lexol IPM (Isopropyl myristate) 1.00

Lexol EHP (Wickenol 155) 2.00

Dow Corning 200 Fluid 200cs 0.50

(polydimethylsiloxane)

Propylparaben 0.10

Parsol 1789(BMDM) 2.00

Titanium dioxide 5.00

Described being prepared as follows:

With A heat phase to 75 ℃.

With B heat phase to 75 ℃.

Under vigorous stirring, A is added to the B phase.

Under agitation, be cooled to room temperature.

Used TiO ₂As follows:

A. the TiO of doped with manganese ₂(level of manganese is to about 1% mol ratio); The primary granule size is 20-30nm; Crystal formation 99% is a rutile; No coating

B. from the Uvinul TiO of BASF ₂

Primary granule size-Yue 21nm

Crystal formation-75% anatase octahedrite/25% rutile

Coating-5% trimethylammonium octyl group silane

MT100AQ is from Tayca Corp

Primary granule size-15nm

Crystal formation-Yue 100% rutile

Coating-alumina/silica/Lalgine, as many as 30%.

Adopt the DPPH analytical technology among the embodiment 1, and use cuvette and adopt the light absorption ratio method of masurement on artificial skin, said preparation to be tested.

Artificial skin

From IMS Testing Group (IMS test group), obtain Vitro-Skin (isolated skin).Vitro-Skin is cut into the rectangle of 6.2 * 9cm, and in the container sealing that contains 15% glycerine, controlling moisture, places and spend the night.Charge capacity with 2mg/ml places opalizer sample (preparation) on the rehydrated film, and with the finger that is coated with latex it is tiled.This film is placed on the non-glass object slide stand of 6 * 6cm, and allows its dry 15 minutes.Measure the UV light absorption ratio, this sample was through xenon arc solar simulator irradiation 2 hours then.Light absorption ratio measuring result when writing down irradiation in 5,15,30,60,90 and 120 minutes subsequently.

Cuvette

With sample pack into (volume of sample is approximately 4 μ l, liquid) in the 10 μ m cuvettes.The UV light absorption ratio and is being measured in the time of 5,15,30,60,90 and 120 minutes through the irradiation of xenon arc solar simulator or SOL2 solar simulator (HonleUV technology) before illumination.Also prepared and be the reference substance of Nivea SPF10.

Analyze for DPPH, described preparation contains 2%Parsol 1789 (avobenzone).

Gained the results are shown among Fig. 1.Obvious described adulterated TiO ₂Remove activity and be better than commercial prod significantly, the loss speed of DPPH is approximately big 3 times.

Fig. 2 shown the preparation that contains 2% avobenzone on the aqueous artificial skin during 0 minute and 120 minutes 360nm the light transmission result.

Fig. 3 has shown that the preparation that contains 2% avobenzone (AVO) and 5% Uvinul MC-80 (OMC) on aqueous artificial skin is in the light transmission result of 360nm.

Fig. 4 has shown the light transmission result of the preparation that contains 2% avobenzone in cuvette 360nm when 0 minute and 120 minutes.

These results clearly illustrate described adulterated TiO ₂Advantage aspect minimizing UVA transmission.At the 0 minute ratio during with 120 minutes was significantly different, and this fact means in the preparation that uses adulterated titanium dioxide, existed the minimizing that produces and remove the free radical charge capacity that two aspects cause from reducing.

The 3rd embodiment

The 3rd embodiment of the present invention relates to the polymeric composition of various uses

Well-known many polymeric composition are subjected to light, particularly the detrimental action of UV light.This can make the multiple physical properties of described composition be affected.Typically, the intensity of solid plastic cement composition is adversely affected, and makes it become more crisp along with the time.Similarly review application is to coating composition.Other character that can be subjected to detrimental action comprises color.For example, as everyone knows the coating composition such as paint is subjected to the detrimental action of light, thus fade, or under the situation of white preparation its colour changed into yellow.

Various trials have been carried out so that stop these detrimental actions.This comprises photostabilizer is joined in the described composition, is generally hindered amine.Yet it is relatively costly and always ineffective especially adding this type of photostabilizer.

The present invention is based on the titanium dioxide that find to add specific type and zinc oxide and can stops effectively and be exposed to light, the detrimental action that is generally in the sunlight to be brought.

Britain at us applies in No. 0310365.2, also has zinc oxide or titanium dioxide or the reductive zinc oxide that is doped with second element in the described composition if we disclose, and then can delay the degraded of polymeric composition.In other words, by using these adulterated materials or reductive zinc oxide rather than common titanium dioxide or zinc oxide, it may for example provide the polymeric composition with better UV photo-protection, perhaps has identical anti-degradation property but contains the composition of the photostabilizer of less amount.Therefore the invention describes polymer composition, the organic or inorganic component that it comprises a certain amount of one or more photosensitive and/or is degraded by other composition in the said composition, and a certain amount of TiO that has been doped with second element ₂And/or ZnO or reductive ZnO.Do not contain the TiO that is doped with second element with removing ₂And/or the composition that has same recipe outside ZnO or the reductive ZnO is compared the deterioration rate of the UV sensitivity of light physical agent of said composition low at least 5%.

" physical agent " means the measurable magnitude of the physical properties of the described composition that is subjected to UV light detrimental action.The example of this type of physical agent comprises degraded and follow-up intensity, colour-change (for example, to paint and textiles) and the stability (for example, to filmstrip) of taking a picture.

Therefore, if the deterioration rate of physical agent is X, then the described deterioration rate that has of the measurer of the organic constituent of the degraded of other composition in the photosensitive and/or the thing that is combined is Y, and wherein Y is bigger at least by 5% than X, adulterated TiO ₂And/or the amount of ZnO and/or reductive ZnO is reduced to X with described rate of loss by Y.The present invention also provides adulterated TiO ₂Purposes in the deterioration rate of the physical agent of the concentration of/ZnO and/or reductive ZnO one or more photostabilizers in reducing polymeric composition and reduction polymeric composition.The present invention also provides the method for the stability of the physical agent that improves composition, described composition contain one or more photosensitivity and/or by the component of the degraded of other composition in the described composition, described method is included in and adds adulterated TiO in the said composition ₂/ ZnO and/or reductive ZnO.

Described in second embodiment, key is if desire to make described oxide compound really effective, then in its surface must existence can with the hotchpotch of the component interaction of desire protection in the described composition.Usually cause some hotchpotchs to be present in this particulate surface or the surface though be used for the adulterated existing method of main body, can use the material of a surface doping according to the present invention, promptly hotchpotch only is present in this particulate surface or on the surface.In one embodiment, this material can be used in the monophasic preparation.

Therefore, the invention provides composition (although not relying on above-mentioned theory), it comprises a certain amount of one or more photosensitive and/or by the organic or inorganic component of the degraded of other composition in the said composition, and a certain amount of at least in its surface or be doped with the TiO of one or more other elements in the surface ₂And/or ZnO, this other element is a kind of only usually, and second element is promptly only arranged.

Described composition can be a polymeric composition, and it means said composition can comprise one or more polymeric materials, and this polymeric material is generally at least 1% of composition weight, is preferably 5%.Said composition can also be solid or liquid.When having polymeric material, said composition can comprise the organic constituent of at least a portion and/or comprise tackiness agent and/or other component of said composition.

When described particle is mixed by main body, then in whole particle, there is hotchpotch usually.On the other hand, when described particle quilt " surface doping " (being that described hotchpotch is only in the surface or on the surface), then there is concentration gradient, for example, make atoms of dopant to titanium or zinc atom ratio that this particle surface place or outermost " skin " are located greater than core or in intracardiac ratio, may be zero here.Usually, described composition has this prescription, does not promptly contain the described TiO that has been doped with second element with removing ₂And/or the composition that has same recipe outside the ZnO compares, the deterioration rate of the UV photosensitivity physical agent of said composition at least low 5%.

" polymeric composition " used herein refers to comprise the composition of one or more polymeric materials.Said composition can be solid or liquid.

In some situation, the present composition contains unadulterated TiO ₂And/or ZnO.Usually, the unadulterated TiO of this class ₂/ ZnO exists as pigment, has the granularity of 100nm at least usually.

Usually solid material comprises polymer/solid, and this polymer/solid comprises three-dimensional body, film and fiber and textiles and fabric, for example clothes and mesh and the foam article of being made by weaving and non-woven fibre; Sometimes the solid of preferred non-fiber.Three-dimensional body comprises those that made by the melt molding method, comprises tubed goods and moulded product.The typical articles that the present invention may be used on generally includes the family expenses material and the material of construction of external application, comprise window shutter and plastics curtain, frame, pipeline and waterways, such as the coating and the facing of soffit plate and plastics roof cladding, it can be shaped as ripple template, door and window frame.Other goods comprise posters plate etc., billboard on for example following object: automobile side and car body and the body part that comprises the collision bumper of car, motorbus and truck, and the top that also can be used for ship, and the superstructure and the hull that are used for ship, the main body that also has grass mower and tractor and yacht is together with the storage vessel such as bottle, jar, drum, bucket and oil and water.Other object comprises garden furniture.In one embodiment, described solid is not transparent.

The film that the present invention may be used on comprises the free-standing film, and non-free-standing

Film such as coating.The free-standing film that the present invention is applied to comprises photographic film, packing film and has the plastic film of sign that usually as advertisement film, it also can be applicable on the posters plate.This class film can contain one or more compositions commonly used that is used for this series products.Thus, photographic film can contain one or more dyestuffs or dye color coupler, and optional silver halide.

Sometimes, polymeric composition itself is not easy to degraded, but said composition is used to protect substrate, or for container, the material that protection is placed in one.Thus, this based composition can contain adulterated TiO ₂And/or ZnO.Example comprises painted and non-pigmented containers, is generally bottle.

Therefore, the present invention also provides free-standing polymer composition or clear coat composition, is used to make composition adjacent thereto to avoid the detrimental action of light, and it comprises the surface and has been doped with the TiO that is at least second element ₂And/or ZnO.In one embodiment, said composition is three-dimensional, and comprises having TiO ₂And/or the top layer of ZnO, but not surface portion is not timber or such as the reconstruct timber of shaving board, glued board or fiberboard and preferred synthetics usually.

Coating composition is typically paint and varnish, its contain in some varnish as activeconstituents or in paint and furniture polish, wax and paste as the polymkeric substance of balustrade; They can be moisture, or the not moisture organic solvent that promptly contains, and in this case, it can be single-phase or heterogenetic, is generally oil-in-water-type or water-in-oil emulsion.This coating composition can be the form of water-resisting agent.These coating compositions can contain one or more compositions commonly used that is used for these products.Some make-up compositions contain one or more polymkeric substance; In the present invention, not too preferred this based composition.

Can be used on polymkeric substance in the present composition and comprise natural and synthetic polymkeric substance, they can be thermoplasticity or heat cured.

Suitable polymers can be homopolymer or multipolymer, and that this multipolymer can be is random, block or graft copolymer; This polymkeric substance can be crosslinked.Typical polymkeric substance can be saturated or unsaturated polymer.Typical polymkeric substance comprises the alkylidene group polymkeric substance, such as ethene and propene polymer, be generally homopolymer, comprise polyethylene, siloxanes and sulfide polymer, polymeric amide as nylon, polyester such as PET, acrylate and methacrylate polymer are as poly-(methyl methacrylate), urethane comprises foam, such as the vinyl polymer (as ABS) of styrene polymer, comprise polystyrene foam, vinyl chloride-base polymer and polyvinyl alcohol, and the engineered thermoplastic polymkeric substance, comprise aromatic(based)polymer, for example Xian Xing aromatic series semi-crystalline polymer (as PEEK and PES).Can adopt fluorinated polymer such as PTFE and poly(vinylidene fluoride).Described polymkeric substance can be heat cured, as Resins, epoxy and resol, urea resin, melamine resin and alkyd resin.

Adoptable natural polymer comprises the cellulose polymer compound in the paper for example, comprises starch, polysaccharide, xylogen and polyisoprene, as natural rubber.

Will be understood that,, can think that these polymkeric substance are that light is stable because some polymkeric substance do not have or do not have tangible change in physical properties being exposed to the UV light time.Therefore, these polymkeric substance are not photosensitivity, and their purposes is not within the scope of the invention.

The typical polymers that is used for different application comprises: polyester, polymeric amide such as the nylon, the acrylic resin that (a) are used for fiber and fabric; (b) be used for the bottle etc. polyester, polyvinyl chloride, polyethylene, polypropylene; (c) be used for polyethylene, polypropylene, the polyvinyl chloride of film (non-activity as wrapping material).

Described composition can contain other composition commonly used as the composition feature of paying close attention to, and comprises inorganic and pigment dyestuff, comprises " common " TiO ₂And/or ZnO, weighting agent and supplement and photostabilizer are generally hindered amine stabilizer.This added ingredients itself may be vulnerable, and the component of being degraded may cause the degraded of other component of described polymkeric substance or described composition.

Can be by contain and do not contain described adulterated TiO with daylight or radiation of visible light ₂Or the composition sample of ZnO, and in the preset time section, detect the spectral response of said composition and measure the speed that the wavelength change of being launched is determined colour-change.For example use the accelerated weathering test of fugitometer (Fadeometer) to can be used for this purpose.

Can be in a similar fashion measure such as the loss speed of determining article intensity of the present invention at the tensile property of the elongation of fracture place or Young's modulus by adopting such as the standard equipment of Instron tester; Equally, quick aging method is favourable.

Though any minimizing of wavelength change or other physical agent all is favourable, but the existence of all wishing described adulterated oxide compound usually makes described velocity of variation reduce at least 5%, preferred reduction at least 10%, more preferably reduce at least 15%, preferred especially reduction at least 20% most preferably reduces at least 40%.

Though should be understood that generally body dopants and surface doping thing or each surface doping thing are identity element (in order to simplify preparation), this might not be must situation (certainly, for reductive zinc oxide, not having body dopants).For example may change described particulate color in this way.The hotchpotch that is applicable to described oxide particle comprise manganese (especially preferred, Mn for example ²⁺But also has Mn ³⁺), vanadium (V for example ³⁺Or V ⁵⁺), chromium and iron, (especially be Sn but spendable other metal comprises nickel, copper, tin ⁴⁺), aluminium, lead, silver, zirconium, zinc, cobalt (especially is Co ²⁺), gallium, niobium (Nb for example ⁵⁺), antimony (Sb for example ³⁺), tantalum (Ta for example ⁵⁺), strontium, calcium, magnesium, barium, molybdenum (Mo for example ³⁺, Mo ⁵⁺Or Mo ⁶⁺) and silicon.These metals can add separately or add with 2 kinds or 3 kinds or more kinds of mixing.Should be appreciated that for effective main body and mix that ionic size must easily be inserted in the described particulate lattice.For this reason, Mn ³⁺, vanadium, chromium and iron is normally the most effective; Mn ²⁺Ionic size compare Ti ⁴⁺Ionic size much bigger, therefore Mn is seldom arranged ²⁺Ion diffusion enters TiO ₂Intracell possibility.On the other hand, for the element that is used for surface doping, there is not this size restriction; Preferred surface doping thing comprises manganese (Mn for example ²⁺), cerium, selenium, chromium and iron.

Can obtain the particle of described surface doping by any standard method that is used to prepare this type of adulterated oxide compound and salt.This comprises technology as described below.Should be appreciated that described hotchpotch not necessarily must exist with oxide form, but may be to exist such as muriatic salt or such as the salt form with oxo-anions of perchlorate or nitrate.But the main body doping techniques also causes some surface dopings usually, and these technology can be used for the present invention.This class technology comprises the technology of curing, by with parent lattice (TiO ₂/ ZnO) particle with at solution or suspension, be generally in the aqueous solution to mix such as muriatic salt or such as second component that the oxo-anions form of perchlorate or nitrate radical exists, it is cured being generally under at least 300 ℃ the temperature subsequently.Can be used for preparing described other approach and comprise J.Mat.Sci. (1997) 36 through adulterated material, the intermediate processing of type described in the 6001-6008, wherein the solution with the salt of hotchpotch mixes with the solution of the alkoxide of described base metal (Ti/Zn), makes this alkoxide be converted into oxide compound the heating of gained mixing solutions subsequently.It is described till the precipitation of adulterated material up to obtaining to continue heating.Preparation method's more details are referring to WO 00/60994 and WO01/40114.

The photosensitivity of the rutile form of known titanium dioxide is not as anatase form, so preferred rutile form.Zinc oxide can be the form (promptly with respect to oxonium ion, having the particle of excessive zine ion) of reductive Zinc oxide particles.

Can obtain adulterated TiO by flame pyrolysis or plasma body approach ₂Or adulterated ZnO, wherein will be suitably the dopant levels hybrid metal that contains precursor be exposed in flame or the plasma body, to obtain required product.

These class particulate more details are referring to WO 99/60994.

Described particulate average primary particle size is generally about 1-200nm, for example about 1-150nm, preferably about 1-100nm, 1-50nm more preferably from about, and 20-50nm most preferably from about.Owing to think that scavenging(action) is catalytic basically, therefore as far as possible little so that its surface-area maximization of advantageously described particle, and area maximization that therefore will be from the teeth outwards through dopant material.Small grain size has the following advantages: it needs the less doping thing, thereby has reduced any colour effect that is caused by this hotchpotch.

Oxide particle used in this invention can have inorganic or organic coating.For example, this particle can scribble the oxide compound such as aluminium, zirconium or element silicon, particularly silica or pure aluminium silicate for example.Metal oxide particle also can be coated with one or more organic materialss, such as polyvalent alcohol, amine, alkanolamine, poly organic silicon compound, and RSi[{OSi (Me) for example ₂} _xOR ¹] ₃, wherein R is C ₁-C ₁₀Alkyl, R ¹For methyl or ethyl and x are the integer of 4-12, hydrophilic polymer, such as polyacrylamide, polyacrylic acid carboxymethyl cellulose and xanthan gum, or tensio-active agent, for example TOPO.If desired, surface doping can combine individually or with the organic or inorganic coating-forming agent by coating technology and carry out.Therefore, for example unadulterated oxide compound can be such as being coated with manganese oxide together with organic or such as the inorganic coating agent of silica.Usually, need not to apply oxide particle so that it is hydrophilic, therefore, for water, this particle can not have coating.But if this particle will place organic or oil phase, their surface needs hydrophobic property or oil-dispersing property.This can realize by for example suitable hydrophobic polymer of direct coating, or indirectly by applying for example oxide coating of silica (it gives hydrophilicity), is hydrophobic molecule then, for example metallic soap or long-chain (C for example ₁₂-C ₂₂) carboxylic acid or its metal-salt, realize such as stearic acid, stearate, particularly aluminum stearate, Aluminum trilaurate and Zinic stearas.

It should be understood that term " coating " is not to be construed as being limited to whole coverings.In fact, because coating can be used as on free radical and the particle surface or the interactional obstacle of interior hotchpotch, useful is incomplete coating usually.Therefore, when the scavenging(action) of hope optimum, preferably this coating should be discontinuous.What however, it should be understood that is, lip-deep hotchpotch still can play the free radical that produces in the cancellation particle, and in this case, coating can be a successive.Because the silane and the silicon coating that can be polymerization or short chain or monomeric silanes are generally successive, not too preferred usually they.Therefore, owing to have the coating fully that the coating of inorganic oxide does not cause particle surface usually, common preferred this coating.

Composition of the present invention can be for single-phase, and perhaps (or butyrous or be generally hydrophobic) of water-based perhaps is heterogeneous.Typical two-phase compositions is oil-in-water-type or water-in-oil-type preparation.For single-phase composite, oxide particle should be dispersed in certainly this mutually in.Therefore, be hydrophilic if composition is this particle of hope of water-based, if composition is based on oil, wish that then this particle is hydrophobic.But may be with untreated TiO by suitable hybrid technology ₂Be dispersed in the oil phase.For two-phase or multiphase composition, this particle should be present in contain the composition that will protect one of (or composition) mutually in.Be present in water (or being generally aqueous favoring) and the oil phase (or being generally mutually hydrophobic) but it is desirable to this particle, even there is not the composition that will protect in these one in mutually in mutually.But but the weight ratio of wishing water discrete particles and oil discrete particles is 1: 4 to 4: 1, and preferred 1: 2 to 2: 1, ideal was the equivalent ratio.

In described composition, the concentration of described metal oxide is preferably about 0.5-20% weight ratio, preferably about 1-10% weight ratio, and 3-8% weight ratio more preferably from about.

The embodiment 1 that provides in above-mentioned first embodiment, following examples are also exemplarily described the present invention.

Embodiment 3

Adulterated TiO ₂Preparation

Coprecipitation method

At room temperature, under agitation condition, with distilled water (170cm ³), dense HCl (12cm ³) and 2-propyl alcohol (12cm ³) mix.The proper metal salt of the per-cent charge capacity calculated is joined (being 1% charge capacity in this example) in this solution.Behind thorough mixing, add titanium isopropylate (10.4cm lentamente with transfer pipet ³).Form gelatinous precipitate at once.After the solution clarification, this solution of heating in water-bath.In several hrs, bath temperature is risen to 328K lentamente from room temperature.The solution placement is spent the night.Inclining gained precipitation and dry under 353K, places several hrs then in the baking oven of 373K.Subsequently with this sample at first when the 873K, (to guarantee to form rutile crystal) calcined 3 hours in air when 1273K subsequently.(heating means: with 200Kelvin/ hour temperature is heated to selected temperature from 298Kelvin, the residence time=3 hour are cooled to 298K with 200K/h subsequently).

Absorption process

With proper metal salt (1% charge capacity) together with TiO ₂Powder Degussa P25 (0.05 mole～75% anatase octahedrite and 25% rutile; Surface-area～50m ²/ g; Mean particle size～30nm) be dissolved in the methyl alcohol.With the solution stirring several hrs, evaporating solvent remains TiO then ₂Powder.When 423K, this powder was placed in baking oven 2-3 hour, adopt the identical heating means in the coprecipitation method in air, to calcine subsequently in 873K.

EPR

In the EPSRC EPR instrument of Cardiff University (Cardiff University), (100K) carries out electron paramagnetic resonance in low temperature.

The adulterated TiO of Mn- ₂, coprecipitation method

Prepare Mn (II)-adulterated TiO by two kinds of preparation methods ₂Sample also obtains their EPR wave spectrum.1%Mn (the II)-adulterated TiO that makes by the co-precipitation approach ₂Wave spectrum show Mn ⁴⁺Occupy the position and the Mn of replacement ²⁺The Space-Occupying position.

The adulterated TiO of Mn- ₂, absorption process

1%Mn (the II)-adulterated TiO that makes by absorption process ₂The Mn that show to replace adds of wave spectrum ⁴⁺Mn ²⁺Replace and add.Also evidence show surperficial Mn ²⁺

The adulterated TiO of V (IV) ₂

Prepare V (IV)-adulterated TiO by two kinds of preparation methods ₂Sample also obtains their EPR wave spectrum.1%V (the IV)-adulterated TiO that makes by the absorption approach ₂Wave spectrum show the wave spectrum of resolution difference, this is because may be because Ti ³⁺Ion makes V ⁴⁺Ion overlaps in the resonance of broadband.1%V (IV)--the adulterated TiO that makes by coprecipitation method ₂Wave spectrum shown the well resolved wave spectrum of the hyperfine line resonance of eight layers (eightfold), this is because V ⁴⁺Occupy this TiO ₂The position of substitution in the matrix makes ⁵¹The magnetic moment and the paramagnetic V of V nuclear ⁴⁺Existing between the ion interacts causes.

The adulterated TiO of V (V) ₂

Prepare V (V)-adulterated TiO by two kinds of preparation methods ₂Sample also obtains their EPR wave spectrum.V (V)-adulterated TiO by prepared by co-precipitation ₂Wave spectrum show V ⁴⁺Occupy the position of replacement, and V (the V)-adulterated TiO that produces by the described precipitator method ₂The wave spectrum that shows the resolution difference, this wave spectrum reflected and had this possibility, and promptly vanadium ion does not replace and enters TiO ₂Lattice in, but be present on the surface.

The preparation of PVC film

To gather (vinylchlorid) and (1g) be dissolved in the tetrahydrofuran (THF) (20cm of HPLC level ³) in, and the TiO of the improvement of adding respective amount ₂Pigment (being 4% charge capacity in this example).Then with this solution ultrasonic/stir about 1 hour.By with the disposable aluminium dish of this solution impouring (area=8.55cm ²) in, and make solvent evaporation prepare this film (100-150 μ m).Obtain and write down the weight (surplus four radix point) of gained disk then.By using known area, weight and the density of this PVC film, from these data, obtain thickness.Examine this thickness by under Olympus BH2 scanning optical microscope, analyzing this film.The record IP spectrum and according to it at 2913cm ^-1Relative light absorption ratio select the size of sample.Under the temperature of 318K, in the QUV weatherometer that is equipped with 8UVB 300W bulb (Q Panel Company), shine this film then.

The UV irradiation apparatus

The weatherometer that uses Q Panel QUV to quicken.This device comes down to UV irradiation pond.Will be as UV _B8 luminescent lamps (300W) that wavelength is selected are installed in this instrument, and the moisture bath also can be used for strengthening exacting terms.Film sample is placed in the next door that this instrument was gone up and be placed on to dish.Use three oxalic acid and close the light intensity that the sour potassium of iron (III) (potassium ferrioxalate) systems measurement is sent in the QUV weatherometer.Intensity on this instrument next door is calculated as 1.82 * 10 ¹⁷Quantum/second.

The result

(scope is 3200cm to use Perkin-Elmer 1000 spectrophotometers ^-1-400cm ^-1) record IR absorption spectrum.At 4cm ^-1The place pre-determines resolving power.Monitoring is also calculated at 1718cm ^-1The appearance of the carbonyl peak at place.Write down the appearance in time of this peak, and according at 2913cm ^-1The CH band calibration at place produces " carbonyl index ".

Add Mn and V to TiO ₂In the results are shown among Fig. 5 to 7 influence of the photodegradation of PVC film." 1%Mn (Co) " adulterated TiO of Mn for making by described coprecipitation method ₂, and " 1%Mn (A) " makes by absorption process; Similarly explain and be applied to the adulterated material of V-.By the carbonyl index of described adulterated sample and the carbonyl index of unadulterated sample are compared, after 500 hours, calculate protection factor.

In Fig. 5, aspect the described PVC film of protection, with described unadulterated TiO ₂Compare, the validity of 1%Mn (coprecipitation method) sample is high about 9%, and the validity of 1%Mn (absorption process) sample high about 23%.In Fig. 6, aspect the described PVC film of protection, with described unadulterated TiO ₂Compare, the validity of 1%V (coprecipitation method) sample is low about 20%, and the validity of 1%V (absorption process) sample high about 12%.In Fig. 7, aspect the described PVC film of protection, with described unadulterated TiO ₂Compare, the validity of 1%V (coprecipitation method) sample is low about 6%, and the validity of 1%V (absorption process) sample high about 6%.

Fig. 8 has shown the effect of the adulterated ZnO (calcining) of interpolation Mn to the PVC film under 573K." LM " and " HM " refers to the Mn of lower concentration and high density." HM31 cal " demonstration is compared with unadulterated ZnO, is improving 27% aspect the protection of PVC film.Compare with described unadulterated reference product, all adulterated materials show more provide protection.

The 4th embodiment

The present embodiment has related to the composition that is applicable to agricultural, gardening and veterinary applications.

The activeconstituents of well-known a lot of animal doctor's usefulness, agricultural and horticultural compositions, for example weedicide and sterilant are subjected to the detrimental action of UV light.This class organic compound is tending towards degrading or resolves into non-active compound or zone to be processed is had the compound of detrimental action under the influence of UV light.Therefore must be in the special container that UV light can't penetrate with these product stock.Otherwise the storage life of this product is very short.

Our Britain of mentioning above-mentioned applies in No. 0312703.2, we disclose and can reduce and/or eliminate the detrimental action of UV light to this class organic compound by add titanium dioxide and/or zinc oxide and/or the reductive zinc oxide that has been doped with second element in described composition.In other words, by in described preparation, adding this special oxide compound, the life-span that may need not to use special container and/or prolong described product.In addition, its existence can make the user use this less product.Therefore the application has described the composition that is applicable to that veterinary science, agricultural or gardening use, it comprises at least a organic veterinary science, active compound agricultural and/or Horticulture, titanium dioxide and/or the zinc oxide and/or the reductive zinc oxide of second element have been doped with, and the method that is used for handling at privileged site described animal doctor, agricultural or gardening species has been described, it comprises with this position of this compositions-treated.

Though the minimizing of any UV absorption loss rate all is favourable, wish that usually the existence of described oxide compound should be reduced by at least 5% with the UV uptake rate, be preferably at least 10%, more preferably at least 15%, especially at least 20%, and most preferably be at least 40%.

According to the present invention, the mode of the described oxide compound of having found to mix has substantial role to the effect of this oxide compound.Really, should understand key now is if desire to make described oxide compound really effective, then in its surface must existence can with the hotchpotch of the component interaction of desire protection in the described composition.For example, if in two-phase compositions, described oxide compound is present in water, and the described component of desire protection is present in organic phase, so then because phase boundary seldom has interaction.Therefore, the free radical that is produced by the Degradation of this component then can not contact described hotchpotch from a phase shift to another phase time.Though the existing adulterated method of main body that is used for also causes some hotchpotch to be present in the described particulate surface or the surface usually, only can use material according to the present invention, promptly only in this particulate surface or on the surface hotchpotch is arranged at surface doping.In one embodiment, this class material can be used in the monophasic aqueous compositions.Therefore, the invention provides the composition that (although not relying on above-mentioned theory) is applicable to that veterinary science, agricultural or Horticulture are used, said composition comprises at least a organic veterinary science, active compound agricultural and/or Horticulture, and at least in its surface or be doped with the titanium dioxide and/or the zinc oxide of one or more other elements on the surface, this other element is generally a kind of, and second element is promptly only arranged.When described particle is that main body is adulterated, then in whole particle, there is hotchpotch usually.On the other hand, when described particle quilt " surface doping " (being that described hotchpotch is only in the surface or on the surface), then there is concentration gradient, therefore atoms of dopant to titanium or zinc atom ratio that this particle surface place or outermost " skin " are located greater than core or in intracardiac ratio, may be zero here.

Though should be appreciated that generally body dopants and surface doping thing or each surface doping thing are identity element (in order to simplify preparation), this might not be necessary situation (certainly, for reductive zinc oxide, not having body dopants).For example may change described particulate color in this way.The hotchpotch that is applicable to described oxide particle comprise manganese (especially preferred, Mn for example ²⁺But also has Mn ³⁺), vanadium (V for example ³⁺Or V ⁵⁺), chromium and iron, (especially be Sn but spendable other metal comprises nickel, copper, tin ⁴⁺), aluminium, lead, silver, zirconium, zinc, cobalt (especially is Co ²⁺), gallium, niobium (Nb for example ⁵⁺), antimony (Sb for example ³⁺), tantalum (Ta for example ⁵⁺), strontium, calcium, magnesium, barium, molybdenum (Mo for example ³⁺, Mo ⁵⁺Or Mo ⁶⁺) and silicon.These metals can add separately or can 2 kinds or 3 kinds or more kinds of mixing addings.Should be appreciated that for effective main body and mix that ionic size must easily be inserted in the described particulate lattice.For this reason, Mn ³⁺, vanadium, chromium and iron is normally the most effective; Mn ²⁺Ionic size compare Ti ⁴⁺Ionic size much bigger, therefore Mn is seldom arranged ²⁺Ion diffusion enters TiO ₂Intracell possibility.On the other hand, for the element that is used for surface doping, there is not this size restriction; Preferred surface doping thing comprises manganese (Mn for example ²⁺), cerium, selenium, chromium, vanadium and iron.

Can determine on the described particle and the optimal amts of (if exist) second component in the particle by normal experiment, enough low but total amount is preferably, thus the particle minimally is colored.Common spendable content is low to moderate 0.1% mol ratio or lower, 0.05% mol ratio for example, or high to 1% mol ratio or higher, for example 5% mol ratio or 10% mol ratio.Typical concentration is a 0.5-2 mole % weight ratio.From the teeth outwards, hotchpotch is generally 2-25 to the mol ratio of matrix metal: 98-75 is generally 5-20: 95-80, and especially be 8-15: 92-85.Hotchpotch content in the surface can be measured by for example sub-spectrography of X-ray photoelectric (XPS).

Can obtain the particle of described surface doping by any standard method that is used to prepare this type of adulterated oxide compound and salt.This comprises technology as described below.Should be appreciated that described hotchpotch not necessarily must exist with oxide form, but may be to exist such as muriatic salt or such as the salt form with oxo-anions of perchlorate or nitrate.But the main body doping techniques also causes some surface dopings usually, and these technology can be used for the present invention.This class technology comprises the technology of curing, by with parent lattice (TiO ₂/ ZnO) particle with at solution or suspension, be generally in the aqueous solution to mix such as muriatic salt or such as second component that the oxo-anions form of perchlorate or nitrate radical exists, it is cured being generally under at least 300 ℃ the temperature subsequently.Other approach that can be used for preparing described dopant material comprises J.Mat.Sci. (1997) 36, the intermediate processing of type described in the 6001-6008, wherein the solution with the salt of hotchpotch mixes with the solution of the alkoxide of described base metal (Ti/Zn), makes this alkoxide be converted into oxide compound the heating of gained mixing solutions subsequently.It is described till the precipitation of adulterated material up to obtaining to continue heating.Preparation method's more details are referring to WO 00/60994 and WO01/40114.

The details that this class particle is further discussed can be referring to WO 99/60994.

Described particulate average primary particle size is generally about 1-200nm, for example about 1-150nm, preferably about 1-100nm, 1-50nm more preferably from about, and 20-50nm most preferably from about.Owing to think that scavenging(action) is catalytic basically, therefore as far as possible little so that its surface-area maximization of advantageously described particle, and make lip-deep area maximization through adulterated material.Small grain size has the following advantages: it needs the less doping thing, thereby has reduced any colour effect that is caused by this hotchpotch.

Composition of the present invention can be single-phase for water-based or butyrous, perhaps is heterogeneous.Typical two-phase compositions is oil-in-water-type or water-in-oil-type preparation.For single-phase composite, oxide particle should be dispersed in certainly this mutually in.Therefore, be hydrophilic if composition is this particle of hope of water-based, if composition is based on oil, wish that then this particle is hydrophobic.But may be with untreated TiO by suitable hybrid technology ₂Be dispersed in the oil phase.For two-phase or multiphase composition, this particle should be present in contain the composition that will protect one of (or composition) mutually in.Be present in water and the oil phase but it is desirable to this particle, even there is not the composition that will protect in these one in mutually in mutually.But but the weight ratio of wishing water discrete particles and oil discrete particles is 1: 4 to 4: 1, and preferred 1: 2 to 2: 1, ideal was the equivalent ratio.

The present invention can be applicable to that any preparation is used for that agricultural or gardening uses comprises organic composition of active components and is applied to comprise organic activeconstituents, is generally the veterinary composition of topical application.Common described activeconstituents is a biocide, but its can for, for example, plant growth promoter or conditioning agent.Therefore, described composition of the present invention is generally weedicide, mycocide, sterilant, sterilant, mitigal agent, molluscacidal agent, miticide or rodenticide, they can be wide spectrum or optionally.The present invention is particularly useful for the sterilant of quick decomposition, and this sterilant that decomposes is fast had a strong impact on by UV light.Veterinary composition can adopt the form of sterilant for example or wound healing preparation.

Composition of the present invention also can be prepared with sterilant and rodenticide, is used for domestic use.Therefore, the present invention also provides the composition that is suitable for domestic use, titanium dioxide and/or zinc oxide that it comprises at least a organic-biological agent for killing and has been doped with second element, and/or reductive zinc oxide.

Composition of the present invention also can contain any organic active composition that is used for this based composition at present.

The available weedicide that is fit in the present invention comprises triazine, aminocompound, particularly halogenated acetanilide being, carbaminate, Tolylamine (dinitraniline), urea, plant growth hormones, particularly phenoxy acid and phenyl ether.Therefore spendable weedicide comprise phenoxy alkane acid, two pyridines, benzonitrile together with phthalic compounds, dinitraniline, acid amides, carbamate, thiocarbamate, comprise the heterocyclic nitrogen compounds of triazine, pyridine, pyridazinone, sulfonylurea, imidazoles and replace urea and halogenation aliphatic carboxylic acid, some are inorganic and organic materials and biologically important amino acid derivative.Available specific weedicide in the present invention comprise the 2,4 dichloro benzene ethoxyacetic acid (2,4-D) and 2,4, the 5-trichlorophenoxyacetic acid (2,4,5-T).The triazine that is fit to comprise 2-chloro-, 2-methyl sulfo--, 2-methoxyl group-4,6-is two-(alkylamino)-s-triazine and some 2-azido--replacement triazine.Typical weedicide urea comprises (3-right-chloro-phenyl-)-1,1-dimethyl urea) and Diuron Tech, neburon, fenuron and chlorxuron.The carbamate that is fit to comprises N-phenylcarbamate and phenylcarbamic acid isopropyl ester (propham) and its derivative that is substituted, comprise m-chloro phenylcarbamic acid isopropyl ester (Y 3), and Herba ainsliaeae yunnanensis, swep, dichlormate and Azac.The thiocarbamate that is fit to comprises EPTC, metamsodium, vernolate, CDEC, pebulate, di_allate, tri_allate, butylate, Hydram, cycloate, thiobencarb and ethiolate.The aminocompound weedicide that is fit to comprises pentanochlor, dicryl, Stam F-34, dipehamid, propachlor, alachlor, CDAA, alanap, Machete, prynachlor and napropamide.The chlorination lipid acid that is fit to comprises trichoroacetic acid(TCA) (TCA), dalapon and 2,2,3-chloropon.The benzoic acid chloride that is fit to comprises Amiben, DCPA, dicamba 98, Niagara 5006 and 2,3,6-TBA.Adoptable phenol weedicide comprises bromoxynil, 4-hydroxyl-3,5-diiodo-benzene formonitrile HCN, DNOC and dinoseb.Adoptable suitable dinitraniline comprises benfluralin, trifluralin, nitralin, oryzalin, isopropaline,2,6-dinitroN,N-dipropylcumidine, dinitramine, fluchloralin, profluralin and butralin.Two pyridines (bypyridinium) weedicide that is fit to comprises diquat and paraquat salts and derivative thereof.

The adoptable suitable sterilant of the present invention comprises derivative and organochlorine insecticide, organic phosphorous insecticide, carboxylamine sterilant and the various insect growth regulator(IGR) of nicotinoid, rotenoid, sabadilla seed and plant ryania speciosa and pyrethroid.

The nicotinoid that is fit to comprises nicotine sulfate and imidocloprid.Pyrethroid has constituted a big class of sterilant, its major part is a synthetic now, comprise Chryson, phenothrin (phenothrin), cyphenothrin, empenthrin, prallethrin, permethrin, Cypermethrin, α Cypermethrin, tetramethrin and δ tetramethrin, comprise their isomer, especially optical isomer and their derivative.The organochlorine insecticide that is fit to comprises DDT (dichloro-diphenyl-trichloro-ethane) and methoxy-DDT and perthane, and lindane, toxaphene, Niran, heptachlor, aldrin, Dieldrin-attapulgite mixture and endrin.The organic phosphorous insecticide that is fit to comprises phosphorothioate esters along, vinyl phosphoric acid, heterocycle enol and the s-methyl heterocyclic phosphorothioate esters along of phosphoric acid and phosphorothioic acid anhydrides, aliphatic phosphorothioate esters along and phenyl phosphorothioate esters along, phenyl phosphorodithioate, phenol.Can mention thiophos, parathion-methyl, isochlorothion, compd 22/190, fenitrothion 95, Tiguvon and fensulfothion and fenchlorphos, cynock, propafos and temephos especially among these.Adoptable suitable carbamate insecticides comprises SevinCarbaryl, carbofuran, Propoxur, dioxacarb, bendiocarb, Mexacarbate, Ro 7-5050 and ethiofencarb.The miticide that is fit to comprises chlorfenethol, chlorobenzilate, Mitigan, tedion, sulfenone, Ovotran, propargite, cyhexatin and dienochlor.

In the sterilant that provides above some are suitable for killing rodent, but adoptable other rodents poisoning agent comprises acute rodenticides poisoning agent and the chronic poisons that comprises antithrombotics; These can be stomach poison, contact poison or fumigant.This class antithrombotics comprises melitoxin, warfarin, Coumatetralyl, coumachlor, difenacoum, Talon, bromadiolone, pindone, diphacinone and chlorophacinone.

Because insect is attacked by a lot of pathogenic agent, can be used on the form that sterilant in the present composition also can be microbial reagent.These comprise bacterial agents, especially bacillus microorganisms, particularly such as bacillus thuringiensis (bacillus thuringiensis, b.t.) bacterial strain, fungal agents, protozoon and the virus of b.t.aizawa, israelensis, kurstaki and tenebrionis.

Can be used on the mycocide that is fit in the present composition and comprise element and thiocarbamate and thiuram (thiurame) derivative, phthalic imidine, trichloromethylthio formyl imines (trichloromethylthiocarboximide), aromatic hydrocarbon and dicarboximide such as sulphur, copper, mercury and tin.Specific example comprises Karbam Black, ziram, thiram, zineb, maneb and zinc manganese ethylenebisdithiocarbamate and dimethyl thiocarbamate and bisdithiocarbamic ethyl.Other available mycocide comprises captan, Phaltan, Difolatan and Pecudin.The aromatic hydrocarbon that is fit to comprises quintozene, dinocap, chloroneb, dicloran, dichlone and m-tetrachlorophthalodinitrile and such as vinclozolin, chlozolinate De oxazolidinedione, such as the glycolylurea of iprodione with such as the succinimide of procymidone.Adoptable other mycocide comprises guanidinesalt such as dodine, such as Delan's quinones, such as chinomethionate De quinoxaline, such as the pyridazine of diclomezine, such as the thiadiazole of etridiazole, such as the pyrroles of fenpiclonil, such as the quinoline of ethoxyquin and such as the triazine of anilazine.Other mycocide of available comprises the mitochondrial respiratory inhibitor, and they are generally anilino formyl class, comprise carbox, oxycarboxin, flutolanil, fenfuram, Mepronil, methfuroxam and metsulfovax.Adoptable other mycocide comprises tubulin (microtubuline) polymerization retarder, comprises Top Form Wormer, fuberidazole, derosal, F-1991 and thiophanate methyl.Other suitable mycocide comprises the sterol biosynthesis inhibitor, comprise the C-14 demethylation inhibitor, as have 1,2,4-triazole group is connected to the triazole species of big lipophilic group by 1-nitrogen, especially triazolone, propiconazole, tebuconazole, cyproconazole and tetraconazole and the flusilazole, myclobutanil, flutriafol and the imibenconazole that are combined with Siliciumatom.Other mycocide of available comprises RNA biosynthesis inhibitor, phosphatide biosynthesis inhibitor, melanochrome biosynthesis inhibitor, mycoprotein biosynthesis inhibitor and cell walls biosynthesis inhibitor.

This based composition can be the liquid or solid form.Liquid composition can be water-based or nonaqueous, and solid form comprises powder or pulvis, particle and tablet.Particularly for the rodents poisoning agent, said composition can be the form of bait, the form of food such as grain especially, and it is in advance through rodents poisoning agent and specific oxide process.

The concentration of activeconstituents can change on a large scale in the composition, but is typically 0.5-95, for example the 1-50% weight ratio.

Composition of the present invention preferably contains the activeconstituents of 0.5%-95% weight ratio (w/w).

The present invention is used for composition that agricultural or gardening uses and contains carrier usually and be beneficial to be applied to pending position, and this pending position for example can be plant, seed or soil, or is beneficial to and deposits, transport or handle.This carrier can be solid or liquid, and is generally gas but is compressed into the material of liquid.

But said composition can for example be the form of emulsion enriched material, solution, oil-in-water emulsion, wettable powder, suspension concentrates, pulvis, particle, water discrete particles, microcapsule and gel.The material that can have other.Such as weighting agent, solvent, solid carrier, surface active cpd (tensio-active agent) and optional solid and/or liquid adjuvants and/or adjuvant.Said composition can be formulated as for example by spraying, atomize, disperse or pouring into and disperse.

Adoptable solvent comprises as replacing the arene of naphthalene (naphthylene), phthalic acid lipid such as dibutyl phthalate or dioctyl ester, fat hydrocarbon such as hexanaphthene or paraffin, alcohols and glycols and their ethers and ester class such as ethanol, glycol monomethyl and dme, ketone such as pimelinketone, intensive polar solvent such as N-N-methyl-2-2-pyrrolidone N-or gamma-butyrolactone, senior alkyl pyrrolidinone compounds such as n-octyl pyrrolidone or cyclohexyl pyrrolidone, epoxidized vegetable oil ester class and water such as methylate coconut grease or soybean grease.Also can use mixture.

But can be used for pulvis, wettable powder, water discrete particles or particulate solid carrier and comprise mineral-filled thing, such as silica, calcite, talcum, kaolin, polynite or attapulgite.Can improve physicals by silicon gel or the polymkeric substance that adds high dispersing.Be used for the particulate carrier and can be porous material, for example float stone, kaolin, sepiolite, wilkinite; The nonabsorbable carrier can be calcite or sand.

Composition can be formulated as enriched material, can be diluted before use by the user subsequently.The existence for the carrier of tensio-active agent in a small amount is beneficial to this dilution.Therefore, composition of the present invention can preferably contain tensio-active agent.For example, said composition can contain two or more carriers, and one of them is planted and is tensio-active agent.This class tensio-active agent can be nonionic, negatively charged ion, positively charged ion or zwitterionics.

Composition of the present invention for example can be formulated as wettable powder, water-dispersible granular material, pulvis, particle, solution, emulsifiable concentrate, emulsion, suspension concentrates and aerosol.Wettable powder contains the activeconstituents of 5-90%w/w and dispersion and/or the wetting agent of 3-10%w/w usually, and if necessary, the stablizer of 0-10%w/w and/or other additive such as permeate agent or tackiness agent.Pulvis is usually formulated as the pulvis enriched material, and the composition of itself and wettable powder is similar but do not have dispersion agent.Water-dispersible granular material is prepared into the size of 0.15mm-2.0mm usually, contains the activeconstituents of 0.5-90%w/w and the additive of 0-20%w/w, for example stablizer, tensio-active agent, slowly-releasing modifier and tackiness agent.Except solvent or solvent mixture, emulsifiable concentrately also contain the activeconstituents of 1-80%w/v, the emulsifying agent of 2-20%w/v and other additive of 0-20%w/v usually, such as stablizer, permeate agent and stopping agent.Suspension concentrates contains the activeconstituents of 5-75%w/v, the dispersion agent of 0.5-15%w/v, the suspension agent such as protective colloid and thixotropic agent of 0.1-10%w/v, other additive of 0-10%w/v usually, for example defoamer, stopping agent, stablizer, permeate agent and tackiness agent, and water or activeconstituents are insoluble to organic liquid wherein substantially; Some organic solid or inorganic salt may be dissolved in the preparation to assist to prevent to precipitate with crystallization or as the frostproofer of water.

The embodiment that provides in above-mentioned first embodiment has also exemplarily described the present embodiment.

Claims

1.TiO ₂Or the particle of ZnO, described particle has been doped with one or more other elements, makes the concentration of hotchpotch in described particle surface greater than the concentration at described granular core place.

2. particle as claimed in claim 1, it is applied by discontinuous wetting ability or hydrophobic material layer.

3. particle as claimed in claim 2, it is applied by hydrophobic polymer.

4. particle as claimed in claim 2, it is at first applied by the oxide compound of aluminium, zirconium or silicon, is applied by the carboxylate salt of long-chain then.

5. prepare each described particulate method in the aforementioned claim, comprise TiO ₂Or the particle of ZnO contacts for some time with the solution or the suspension of the salt of described hotchpotch, cures the gained particle then, and wherein said for some time deficiency is so that the concentration of hotchpotch salt in described granular core reaches its concentration at described particle surface place.

6. method as claimed in claim 5, wherein said particle cures under at least 500 ℃ temperature.

7. by each described particle in the claim 1 to 5 of each described method preparation in the claim 5 or 6.

8. be applicable to the UV sunscreen composition that makeup or part drug use, it comprises:

(a) one or more organic constituents, this organic constituent are photosensitive and/or are easy to by other composition of described composition and/or unadulterated TiO ₂And/or unadulterated ZnO degrades; And

(b) surface doping has the TiO of one or more other elements ₂And/or ZnO.

9. composition as claimed in claim 8, it is an aqueous formulation, and described TiO ₂And/or ZnO only is a surface doping.

10. composition as claimed in claim 8 or 9, it is an Oily preparation.

11. composition as claimed in claim 8 or 9, it is oil-in-water-type or water-in-oil-type preparation.

12. composition as claimed in claim 11, wherein said TiO ₂And/or ZnO exists in two-phase.

13. as each described composition in the claim 8 to 12, wherein said TiO ₂And/or ZnO is applied by discontinuous wetting ability or hydrophobic material layer.

14. composition as claimed in claim 13, wherein said TiO ₂And/or ZnO is applied by hydrophobic polymer.

15. composition as claimed in claim 13, wherein said TiO ₂And/or ZnO at first applies by the oxide compound of aluminium, zirconium or silicon, applied by the carboxylate salt of long-chain then.

16. as each described composition in the claim 8 to 15, wherein one or more described organic constituents are the UV opalizer.

17. composition as claimed in claim 16, wherein said organic opalizer absorbs the UV light in the UVA district.

18. as claim 16 or 17 described compositions; wherein said organic opalizer is para-amino benzoic acid, its ester or derivatives thereof, Methoxycinnamate, benzophenone, phenyl phenacyl ketone, alkyl-β, beta-phenyl acrylate, triazine, camphor derivatives, organic pigment, based on opalizer or 2-Phenylbenzimidazole base-5 sulfonic acid or the phenyl bisbenzimidazole base sulfonic acid of silicone.

19. as each described composition in the claim 8 to 18, it comprises one or more following materials:

Fatty substance, organic solvent, silicone, thickening material, negative catalyst, the UVB opalizer, defoamer, wetting agent, spices sanitas, surface active weighting agent, sequestrant, negatively charged ion, positively charged ion, nonionic or amphiphilic polymers, propelling agent, basifier or souring agent, tinting material or metal oxide pigment.

20. as each described composition in the claim 8 to 19, it is an opalizer.

21. each defined adulterated TiO in the aforementioned claim ₂The purposes of/ZnO, described purposes is the concentration of other composition of reducing one or more organic UV opalizers in the UV sunscreen composition or photosensitive and/or being degraded by another composition.

22. be used to increase the method for the validity of organic UV sunscreen composition, described composition comprises one or more photosensitive and/or is easy to by other composition of described composition and/or unadulterated TiO ₂And/or the component that unadulterated ZnO degraded, described method comprises each defined adulterated TiO in the aforementioned claim ₂/ ZnO adds in the described composition.

23. reduce the method that the toxic chemical in the UV sunscreen composition generates, described method comprises each defined adulterated TiO in the aforementioned claim ₂And/or ZnO adds in the described UV sunscreen composition.

24. composition, it comprises a certain amount of one or more photosensitive and/or by the organic or inorganic component of other composition of described composition degraded, and a certain amount of at least in its surface or be doped with the TiO of one or more other elements in the surface ₂And/or ZnO.

25. composition as claimed in claim 24, the deterioration rate of the UV photosensitivity physical agent of described composition do not contain the described TiO that has been doped with second element with removing ₂And/or the composition that has same recipe outside the ZnO compares low at least 5%.

26. composition as claimed in claim 25, wherein said physical agent are tensile strength.

27. composition as claimed in claim 25, wherein said physical agent are color.

28. as each described composition among the claim 8-27, it contains unadulterated TiO ₂And/or ZnO, randomly be unadulterated TiO ₂And/or ZnO particle.

29. composition as claimed in claim 28, wherein said TiO ₂And/or ZnO exists as pigment.

30. as each described composition among the claim 8-29, it is the form of the additive in coating on the polymeric material and/or the polymeric material, described material is thermoplasticity or thermoset or photosensitivity.

31. as each described composition among the claim 8-30, it is the form of three-dimensional article or for the form of film or for the form of photographic film or for the form of coating composition or be the paint or the form of varnish.

32. the free-standing polymeric composition, it is used to protect composition adjacent thereto to avoid the detrimental action of light, and described polymeric composition comprises at least in the surface or is doped with the TiO of one or more other elements on the surface ₂And/or ZnO, perhaps reductive ZnO.

33. composition as claimed in claim 32, wherein said TiO ₂And/or ZnO is present in the top layer.

34. composition as claimed in claim 33, wherein its non-top layer is not a timber.

35. as claim 33 or 34 described compositions, wherein its non-top layer is a synthetic.

36. clear coat composition, it comprises at least in the surface or is doped with the TiO of one or more other elements on the surface ₂And/or ZnO, perhaps reductive ZnO.

37. as each described composition among the claim 32-36, it has the described feature of one or more claims 25-31.

38. the TiO of each defined surface doping in the claim as described above ₂The purposes of/ZnO, described purposes is for reducing the concentration of one or more photostabilizers in the polymeric composition.

39. the TiO of each defined surface doping in the claim as described above ₂The purposes of/ZnO, described purposes is for reducing the deterioration rate of the photosensitivity physical agent in the polymeric composition.

40. the method for the stability of the physical agent of improvement polymeric composition, described polymeric composition comprises one or more photosensitive and/or by the component of other composition degraded of described composition, described method comprises the TiO with each defined surface doping in the aforementioned claim ₂/ ZnO adds in the described composition.

41. be fit to the composition of animal doctor, agricultural or horticultural applications, it comprises at least a organic veterinary science, agricultural and/or Horticulture active compound, and at least in the surface or be doped with the titanium dioxide and/or the zinc oxide of one or more other elements on the surface.

42. composition as claimed in claim 41, wherein said active compound are weedicide, mycocide, sterilant, mitigal agent, miticide or rodenticide.

43. be fit to the composition that family uses, it comprises at least a organic-biological agent for killing, and at least in the surface or be doped with the titanium dioxide and/or the zinc oxide of one or more other elements on the surface.

44. each described composition or particle or method or purposes in the claim as described above, wherein said hotchpotch is manganese, selenium, cerium, chromium, vanadium or iron.

45. each described particle or composition or method or purposes in the claim as described above, wherein said hotchpotch is Mn ²⁺Or other form of manganese, or be V ⁴⁺

46. each described composition or particle or method or purposes in the claim as described above, wherein said hotchpotch exists with the amount of 0.05% to 10% mol ratio.

47. composition as claimed in claim 46 or particle or method or purposes, wherein said hotchpotch exists with 0.5% to 2% molal weight ratio.

48. each described composition or particle or method or purposes in the claim as described above, wherein said adulterated oxide compound is adulterated titanium dioxide.

49. each described composition or particle or method or purposes in the claim as described above, wherein said titanium dioxide is rutile form.

50. as each described composition or method or purposes among the claim 8-49, it contains reductive zinc oxide.

51. each described composition in the composition claim as described above, it comprises the described adulterated titanium dioxide and/or the zinc oxide of 0.5% to 20% molal weight ratio.

52. each described composition or particle or method or purposes in the claim as described above, wherein said adulterated or reductive oxide compound has the granularity of 1nm to 200nm, is preferably the granularity of 1nm to 100nm; The granularity that perhaps has 100nm to 500nm.

53. composition as claimed in claim 42, wherein said active compound are sterilant.

54. each described composition in the composition claim as described above, it contains one or more weighting agents, organic solvent or tensio-active agent.

55. each described composition in the composition claim as described above, it is the form of water-based or non-aqueous liquid, powder, particle or tablet.

56. the TiO of each defined surface doping in the aforementioned claim ₂The purposes of/ZnO, described purposes is for reducing the concentration of one or more veterinary science, agricultural and/or Horticulture active compound in the composition that is applicable to animal doctor, agricultural, gardening or family's use.

57. the TiO of each defined surface doping in the aforementioned claim ₂The purposes of/ZnO, described purposes is for increasing the storage life of one or more veterinary science, agricultural and/or Horticulture active compound in the composition that is applicable to animal doctor, agricultural, gardening or family's use.

58. increase the method for the validity of the composition that is applicable to that animal doctor, agricultural, gardening or family use, described method comprises one or more organic veterinary science, agricultural or Horticulture or family expenses active compound, and described method comprises the TiO with each defined surface doping in the aforementioned claim ₂/ ZnO adds in the described composition.

59. handle the method for agricultural or gardening species in a position, described method comprises with each described position of described compositions-treated in the foregoing claim.

60. each described particle or composition or method or purposes in the claim as described above are that 2-25 compares 98-75 at the surface hotchpotch to the mol ratio of matrix metal wherein.

61. particle as claimed in claim 60 or composition or method or purposes are that 8-75 compares 92-25 at the surface hotchpotch to the mol ratio of matrix metal wherein.

62. each described particle or composition or method or purposes in the claim as described above, wherein the concentration of hotchpotch in described particulate surface is greater than in the intravital concentration of described particulate master.

63., wherein in described particulate core place and/or described particulate main body, do not have hotchpotch as each described particle or composition or method or purposes among the claim 1-61.

64. there are hotchpotch in each described particle or composition or method or purposes in the claim in the wherein said particulate main body as described above, and described body dopants is different from described surface doping thing or wherein any.

65. respectively as claim 1; 8,24,32,36,41 or 43; 22,23,40,58 to 59; Or 21,38,39,56 or 57 described particle or composition or method or purposes, it is as described herein basically, if desired can be with reference to arbitrary accompanying drawing.