Fiber product which supports photocatalyst, and method for producing same

Textiles which supported the photocatalyst, and a manufacturing method for the same

0001The present invention relates to textiles which supported the photocatalyst, and a manufacturing method for the same, and relates to textiles with the photocatalyst function excellent in especially wash endurance.

0002In recent years, textiles, such as textiles, knitting, and a nonwoven fabric, are made to support a photocatalyst, and giving sterilization, disinfection, and the mildew resistant effect to textiles is performed briskly. That is, the photocatalyst made to exist in a fiber surface absorbs ultraviolet rays, demonstrates strong oxidization power, decomposes a contaminant and a bad smell, and reveals sterilization, disinfection, and the mildew resistant effect. However, if the photocatalyst which reveals strong oxidization power, such as titanium oxide, is used, the textiles themselves which constitutes textiles will be damaged, and causing the strength reduction of the textiles themselves and characteristic degradation is also known.

0003Therefore, the art of isolating a photocatalyst and textiles substrates, such as titanium oxide, is proposed variously, for example, patent documents 1 are, After covering titanium oxide with porous calcium phosphate, the art fixed to textiles with the binder which consists of melamine resin was proposed, and patent documents 2 pasted up the transparent corrosion-resistant tunic which becomes a textiles substrate from a fluoro-resin, and have proposed the art which forms a photocatalyst layer in the outer layer of the corrosion-resistant tunic. However, since the surface of the textiles which constitute a textiles substrate is covered with resin as a result, any proposal of these has the fault that original Texture which textiles have will be spoiled.

<p num="0004"><patcit num="1"><text>JP,2000-119957,A</text></patcit><patcit num="2"><text>JP,10-216210,A</text></patcit></p>

<p num="0005">Therefore, the issue which the present invention tends to solve is providing textiles which the optical damage to a textiles substrate was prevented, and also have original Feel of textiles, and a manufacturing method for the same while having the outstanding photocatalyst function.<br />It is providing textiles which it has the outstanding photocatalyst function, and the outstanding photocatalyst function's moreover has the wash endurance which cannot fall easily due to a repeated wash, and it had in and [ of textiles / original / Feel potato ], and a manufacturing method for the same.</p>

<p num="0006">The place which did various researches that this artificer should solve the above-mentioned subject,<br />(a) Composition formula Zr (HPO)_４-nH_２The crystalline material phosphoric acid zirconium (CZP) denoted by O (n= 0-8) is [Zr._n(PO_４）_2n]^2n-They are each tabular polymers ([Zr) by coming out, and the tabular polymers expressed having the stratified structure piled up mutually, making water distribute the crystalline material phosphoric acid zirconium (CZP) concerned, and performing ionic exchange by an alkali substance._n(PO_４）_2n]^2n-(henceforth a "phosphoric acid zirconium layer") It exfoliates and phosphoric acid zirconium monolayer exfoliation dispersion liquid are obtained,<br />(b) If a textiles substrate is contacted to phosphoric acid zirconium monolayer exfoliation dispersion liquid, a phosphoric acid zirconium layer can combine with a textiles substrate electrostatically,<br />(c) The fact that a photocatalyst may be electrostatically fixed to a phosphoric acid zirconium layer by contacting a phosphoric acid zirconium layer to the water dispersion of a photocatalyst (suitably fixed electrostatic and in covalent bond),<br />(d) If the textiles substrate which introduced the anionic machine or the cationic machine into the fiber surface is contacted in solution of aqueous aluminum compounds, such as alum solution, and also phosphoric acid zirconium monolayer exfoliation dispersion liquid are made to contact, a phosphoric acid zirconium layer can join together electrostatic more firmly via aluminum ion or poly aluminum ion to a textiles substrate -- and<br />(e) A phosphoric acid zirconium layer is laminated on multiplex by using aluminum ion or poly aluminum ion as a binder, It came to complete the present invention by finding out that it can become the structurally stable layered product which between adjoining layers combined firmly electrostatically, and advancing research further based on this knowledge.</p><p num="0007">That is, the present invention is as follows.<br />(1) The textiles which are characterized by fixing a phosphoric acid zirconium layer to a textiles substrate electrostatically, and coming to fix a photocatalyst to the surface of the phosphoric acid zirconium layer electrostatically and which supported the photocatalyst.<br />(2) The textiles of the above-mentioned (1) statement in which aluminum ion or poly aluminum ion intervenes between a phosphoric acid zirconium layer and a textiles substrate.<br />(3) In two phosphoric acid zirconium layers, the phosphoric acid zirconium multiplex layer containing at least one or more laminating sections laminated via aluminum ion or poly aluminum ion, The textiles which are characterized by being electrostatically fixed to a textiles substrate and coming to fix a photocatalyst to the phosphoric acid zirconium layer of the outermost layer of the phosphoric acid zirconium multiplex layer electrostatically and which supported the photocatalyst.<br />(4) The textiles of the above-mentioned (3) statement in which aluminum ion or poly aluminum ion intervenes between a phosphoric acid zirconium multiplex layer and a textiles substrate.<br />(5) Textiles given in either of above-mentioned (1) - (4) whose photocatalysts are titanium oxide.<br />(6) Textiles given in either of above-mentioned (1) - (5) to which a textiles substrate performs anionic machine introduction processing in a fiber surface.<br />(7) The textiles of the above-mentioned (6) statement whose anionic machine is a phosphate group, a carboxyl group, or a hydroxyl group.<br />(8) Textiles given in either of above-mentioned (1) - (5) to which a textiles substrate performs cationic machine introduction processing in a fiber surface.<br />(9) The textiles of the above-mentioned (8) statement whose cationic machine is a quarternary-ammonium-salt machine.<br />(10) after immersing a textiles substrate in solution of an aqueous aluminum compound and washing it -- or It dries, after immersing a textiles substrate in phosphoric acid zirconium monolayer exfoliation dispersion liquid and washing it, without doing the immersion to solution of an aqueous aluminum compound and flush work of this textiles substrate, The 1st process of producing the compound thing which the phosphoric acid zirconium layer united with the textiles substrate via direct or aluminum ion or poly aluminum ion,<br />A manufacturing method of the textiles which supported the photocatalyst which washes and has at least the 2nd process of performing dryness and sintering after a photocatalyst immerses the above-mentioned compound thing in the photocatalyst water dispersion which was charged right and distributed.<br />(11) a textiles substrate is immersed in solution of an aqueous aluminum compound, and the 2nd work is done twice [ at least ] or more in the 1st work to wash and the 2nd work that immerses a textiles substrate in phosphoric acid zirconium monolayer exfoliation dispersion liquid, and washes it -- as The textiles substrate repeatedly processed by turns so that the 2nd work might turn into the last work is dried, The 1st process of obtaining the compound thing which the phosphoric acid zirconium multiplex layer containing one or more laminating sections on which two phosphoric acid zirconium layers were laminated via aluminum ion or poly aluminum ion united with the textiles substrate via aluminum ion or poly aluminum ion,<br />A manufacturing method of the textiles which supported the photocatalyst which a photocatalyst immerses and washes the above-mentioned compound thing to the photocatalyst water dispersion which was charged right and distributed, and has at least the 2nd process of performing dryness and sintering.<br />(12) A manufacturing method of the textiles the above (10) or given in (11) in which a textiles substrate performs anionic machine introduction processing to a fiber surface.<br />(13) A manufacturing method of the textiles of the above-mentioned (12) statement whose anionic machine is a phosphate group, a carboxyl group, or a hydroxyl group.<br />(14) A manufacturing method of the textiles the above (10) or given in (11) in which a textiles substrate performs cationic machine introduction processing to a fiber surface.<br />(15) A manufacturing method of the textiles of the above-mentioned (14) statement whose cationic machine is a quarternary-ammonium-salt machine.<br />(16) A manufacturing method of textiles given in either of above-mentioned (10) - (15) whose aqueous aluminum compounds are alum.</p>

<p num="0008">In the textiles which supported the photocatalyst of the present invention, From the phosphoric acid zirconium and the water-soluble aluminium compound which touch a textiles substrate in a finished product or its manufacturing stage being a comparatively un-active substance, The quality of textiles is hard to be changed, original Texture of textiles can be maintained, moreover, resin etc. do not adhere to the outermost photocatalyst but the photocatalyst function (the grant effects, such as sterilization, disinfection, and mildewproofing) is exhibited efficiently.</p><p num="0009">It is since a photocatalyst is fixed to a phosphoric acid zirconium layer (or phosphoric acid zirconium multiplex layer) electrostatic and in covalent bond, A photocatalyst coating layer with high washing fastness can be formed in the outermost surface, and it is that aluminum ion or poly aluminum ion intervenes between a phosphoric acid zirconium layer (or phosphoric acid zirconium multiplex layer) and a textiles substrate further, In order that a phosphoric acid zirconium layer (or phosphoric acid zirconium multiplex layer) and a textiles substrate may join together firmly, even if it washes textiles, high wash endurance is acquired that a phosphoric acid zirconium layer (or phosphoric acid zirconium multiplex layer) does not drop out [ as a result ] of a textiles substrate easily (namely, -- a photocatalyst is omitted from a product -- hard).</p><p num="0010">When it is the mode by which the photocatalyst was fixed to the phosphoric acid zirconium layer of the outermost layer of a phosphoric acid zirconium multiplex layer, A textiles substrate cannot be subject to the influence of the oxidization power of a photocatalyst more easily, and since the weatherability of the textiles substrate itself is also improved and a textiles substrate moreover becomes more difficult to deteriorate, wash endurance improves further further.</p>

0011<figref num="1">It is a schematic cross section of the 1st mode of the textiles which supported the photocatalyst of the present invention.</figref><figref num="2">It is a schematic cross section of the 2nd mode of the textiles which supported the photocatalyst of the present invention.</figref><figref num="3">It is a schematic cross section of the 3rd mode of the textiles which supported the photocatalyst of the present invention.</figref>

0012Hereinafter, it is based on the suitable embodiment and the present invention is explained.<br />Drawings 1-3 are sectional views showing typically the 1st - the 3rd mode of the textiles (it is also only hereafter called "textiles" for short.) which supported the photocatalyst of the present invention, respectively.

0013The textiles (Drawing 1) of the 1st mode consist of composition that phosphoric acid zirconium layer 2 was electrostatically fixed to textiles substrate 1, and photocatalyst 3 was electrostatically fixed to it by the surface of the phosphoric acid zirconium layer 2.

0014The textiles (Drawing 2) of the 2nd mode are different from the textiles of the 1st mode in that aluminum ion or poly aluminum ion 4 was made to intervene between textiles substrate 1 and phosphoric acid zirconium layer 2.

0015The textiles (Drawing 3) of the 3rd mode have phosphoric acid zirconium multiplex layer 10 in which two phosphoric acid zirconium layers 2 contain at least one or more laminating sections laminated via aluminum ion or poly aluminum ion 4, Phosphoric acid zirconium layer 2a of the innermost layer of phosphoric acid zirconium multiplex layer 10 is electrostatically fixed to textiles substrate 1 via aluminum ion or poly aluminum ion 4, It consists of composition that photocatalyst 3 was electrostatically fixed to phosphoric acid zirconium layer 2b of the outermost layer of phosphoric acid zirconium multiplex layer 10.

0016Drawings 1-3 are although it is the figure simplified for the facilities of explanation and photocatalyst processing is performed only to one principal surface of textiles substrate 1, In fact, it may perform photocatalyst processing (fixation of a phosphoric acid zirconium layer, a photocatalyst, etc.) to both the principal surfaces of textiles substrate 1, and not the whole textiles substrate 1 but sometimes performs photocatalyst processing (fixation of a phosphoric acid zirconium layer, a photocatalyst, etc.) partially according to the form and use of textiles.

0017[Phosphoric acid zirconium layer]<br />Much more tabular polymers that exfoliated with the "phosphoric acid zirconium layer" in the present invention from the crystalline material phosphoric acid zirconium (CZP) which has stratified structure as above-mentioned ([Zr)_n(PO_４）_2n］^2n-They are things. Crystalline material phosphoric acid zirconium (Zr (HPO)) in which a phosphoric acid zirconium layer has stratified structure, for example_４-nH_２Water is made to distribute O (n= 0-8) by shake, and also it is tetra-alkylammonium. Ionic exchange is carried out with the alkaline chemicals consisting of hydroxide, such as (for example, tetramethylammonium, tetraethyl ammonium, tetrapropylammonium, tetrabutylammonium, etc.), etc., and it is each phosphoric acid zirconium layer ([Zr) from crystalline material phosphoric acid zirconium (CZP)._n(PO_４）_2n］^2n-It can obtain by preparing the phosphoric acid zirconium monolayer exfoliation dispersion liquid made to exfoliate. Specifically, tetra n-butyl ammonium solution 1mL of 0.5M is slowly dropped at the water dispersion (0.15g / 20mL dispersion liquid) of crystalline material phosphoric acid zirconium, for example, maintaining pH 8, The solution finally obtained is settled and the supernatant fluid is extracted as exfoliation dispersion liquid by centrifuging (3000 rpm, about 10 minutes).

0018In crystalline material phosphoric acid zirconium (CZP), it is alpha type (Zr (HPO))._４）_２2H_２O) and gamma type (Zr (PO))_４)(H_２PO_４-2H_２Although O) is known, gamma type has a structurally large distance between layers of the number of Price, and it is Na.^＋- Cs^＋intercalating between until layers is possible. On the other hand, alpha type has a little narrow distance between layers, and the intercalation of a between [ layers ] does not happen easily relatively. While gamma type has the partial structure of a phosphate ion and phosphoric acid 2 hydrogen ion, it is thought that alpha type is distributed homogeneously [ since it consists only of partial structure of hydrogen phosphate ion / the charge density on the surface of a layer is more homogeneous, and / adsorption of ion ], and uniform, and a firmer combination can be expected. Therefore, it is preferred to use the phosphoric acid zirconium layer which exfoliated from alpha type crystalline material phosphoric acid zirconium.

0019In the above-mentioned phosphoric acid zirconium monolayer exfoliation dispersion liquid, it is a phosphoric acid zirconium layer ([Zr)._n(PO_４）_2n]^2n-It is charged negatively underwater, and by contacting the textiles substrate just underwater charged in the dispersion liquid, it is distributing, and a phosphoric acid zirconium layer joins together electrostatically, and is fixed to a textiles substrate.

0020Since phosphoric acid zirconium layer 2 intervenes between textiles substrate 1 and photocatalyst 3, textiles substrate 1 is protected from the oxidization power of photocatalyst 3 by the textiles of the present invention. However, the thickness of phosphoric acid zirconium layer (much more) 2 is about 0.75 nm. Therefore, the mode (Drawing 2, three references) which made aluminum ion or poly aluminum ion 4 intervene between textiles substrate 1 and phosphoric acid zirconium layer 2 and/ Or phosphoric acid zirconium layer 2 is considering it as the mode (refer to Drawing 3) phosphoric acid zirconium multiplex layer 10 laminated on multiplex via aluminum ion or poly aluminum ion 4 having been formed, estrangement of photocatalyst 3 and textiles substrate 1 -- distance becomes large, the protection effect of textiles substrate 1 from the oxidization power of photocatalyst 3 can be heightened further, and degradation of a textiles substrate is controlled on a higher level. By carrying out like this, the associative strength of phosphoric acid zirconium layer 2 (or phosphoric acid zirconium multiplex layer 10) to textiles substrate 1 is maintained stably, and the wash endurance of a product improves more.

0021[Aluminum ion or poly aluminum ion]<br />As mentioned above, in the textiles of the present invention, Although the phosphoric acid zirconium multiplex layer on which made aluminum ion or poly aluminum ion intervene between a textiles substrate and a phosphoric acid zirconium layer, and it made the phosphoric acid zirconium layer laminate via aluminum ion or poly aluminum ion suitably is used, Aluminum ion or poly aluminum ion is supplied by contacting solution of aqueous aluminum compounds, such as alum, in a textiles substrate or a phosphoric acid zirconium layer, and drying. A textiles substrate and a phosphoric acid zirconium layer are combined electrostatic more firmly because aluminum ion or poly aluminum ion intervenes between a textiles substrate and a phosphoric acid zirconium layer. This is considered for aluminum ion or poly aluminum ion, and the phosphate group in phosphoric acid zirconium to form a complex. Between adjoining phosphoric acid zirconium layers is electrostatically combined firmly from aluminum ion or poly aluminum ion, and the phosphate group in phosphoric acid zirconium forming a complex also in a phosphoric acid zirconium multiplex layer.

0022As the aqueous aluminum compound which is a source of supply of aluminum ion or poly aluminum ion, For example, a viewpoint to the alum in which the solution which alum, poly aluminum sulfate, aluminum sulfate, an aluminium chloride, the poly aluminium chloride, etc. are mentioned, and does not form precipitation in the range weak alkaline - neutral - weak acidic especially is obtained is preferred. As alum containing aluminum, it is Potash alum (AlK (SO))._４）_２12H_２O), ammonium alum (AlNH)_４(SO_４）_２12H_２O), sodium alum (AlNa (SO))_４）_２12H_２Although O) etc. are mentioned, it is Potash alum (AlK (SO)) from a point of compatibility with phosphoric acid zirconium._４）_２12H_２O) is preferred.

0023In between the adjoining phosphoric acid zirconium layers between a textiles substrate and a phosphoric acid zirconium layer and in a phosphoric acid zirconium multiplex layer, If there are too few amounts of interventions of aluminum ion or poly aluminum ion, It becomes the tendency for the associative strength between a textiles substrate and a phosphoric acid zirconium layer and between adjoining phosphoric acid zirconium layers to decline, and if too large, aluminum ion or the poly aluminum ion itself will drop out of a textiles substrate or phosphoric acid zirconium layer 2 easily. Therefore, the amount of interventions of aluminum ion or poly aluminum ion is 10-100 microg/m.^２But -- desirable -- more -- desirable -- 30-75 microg/m^２It comes out.

0024[Phosphoric acid zirconium multiplex layer]<br />Phosphoric acid zirconium multiplex layer 10 is the structurally stable layered product which between adjoining phosphoric acid zirconium layers combined firmly electrostatically from aluminum ion or poly aluminum ion intervening between adjoining phosphoric acid zirconium layers 2. Although limitation in particular is not carried out, as for the number of layers of phosphoric acid zirconium layer 2 in phosphoric acid zirconium multiplex layer 10, about 2-100 layers are preferred, and, generally, its about 5-10 layers are more preferred. That is, much more thickness of a phosphoric acid zirconium layer is, when the thickness of the aluminum ion of a layer gap or poly aluminum ion is taken into consideration, since there is about 0.75 nm as above-mentioned, As for the total thickness of phosphoric acid zirconium multiplex layer 10, about 2-500 nm is preferred, its about 3-100 nm is more preferred, and especially its about 5-50 nm is preferred. The capability for the total thickness to defend damage to the substrate by the oxidization power of a photocatalyst in less than 2 nm may not fully be acquired, phosphoric acid zirconium multiplex layer 10 exfoliates [ when larger than 500 nm, original Texture of a textiles substrate is spoiled, or ] easily, and there is a possibility that wash endurance may fall.

0025[Textiles substrate]<br />In the textiles of the present invention, textiles substrates are the single fiber which consists of various natural fibers and/or synthetic fibers, Twisted yarn, compound thread, a hollow fiber, a staple, textiles, knitting, a network, a nonwoven fabric, cotton, etc., and neither the kind of textiles nor the form in particular of a substrate is limited.

0026As a natural fiber, animal hairs, such as a cellulosic fiber, wool, cashmere, and Angora, silk, etc. are mentioned, and it is in a cellulosic fiber, for example, Regenerated cellulose textiles, such as viscose rayon, cuprammonium rayon, acetate, etc. besides natural cellulose fibers, such as cotton, hemp, a kenaf, and pulp, etc. are mentioned. As a synthetic fiber, they are acrylic textiles, such as acrylics and modacryl, Polyolefin fibers, such as nylon system textiles, such as polyester fiber, nylon 6, and Nylon 66, polyethylene, and polypropylene, a polyamide fiber, polyimide system textiles, a polyvinyl chloride fiber, vinylon textiles, a polyurethane fiber, etc. are mentioned.

0027Textiles for which the main composition textiles of a textiles substrate are just charged underwater (for example, nylon system textiles) It is giving the substrate to phosphoric acid zirconium monolayer exfoliation dispersion liquid as it is in the case of the textiles substrate consisting of a polyamide fiber, polyimide system textiles, a polyurethane fiber, wool, silk, animal hairs, etc. with which the surface is just charged underwater, and drying, Phosphoric acid zirconium layer 2 electrostatically united to substrate 1 can be formed.

0028in the case of the textiles substrate which consists of textiles (for example, cotton, cellulose, polyester, polyvinyl alcohol, polyether, etc.) negatively charged in underwater in main composition textiles on the other hand and whose surface is charged negatively underwater, it mentioned above -- as After making aluminum ion or poly aluminum ion stick to the surface of a textiles substrate, it is giving a substrate to phosphoric acid zirconium monolayer exfoliation dispersion liquid, and drying, Phosphoric acid zirconium layer 2 is electrostatically fixed via aluminum ion or poly aluminum ion 4 to substrate 1.

0029In the case of the textiles substrate which consists of protein system textiles, such as animal hairs, such as wool, cashmere, and Angora, main composition textiles mention below, After making polyphenol, such as gallic acid, adsorb and also making aluminum ion or poly aluminum ion adsorb, it is giving a substrate to phosphoric acid zirconium monolayer exfoliation dispersion liquid, and drying, Phosphoric acid zirconium layer 2 is electrostatically fixed via aluminum ion or poly aluminum ion 4 to substrate 1.

0030Therefore, the textiles of the mode of Drawings 2 and 3 can be obtained irrespective of the underwater electrification polarity of a textiles substrate. "The main composition textiles of a textiles substrate" in the above is composition textiles which occupy 50 - 100 mass % of the whole textiles substrate.

0031In the present invention, in order to heighten more the associative strength of the phosphoric acid zirconium layer to a textiles substrate, it is preferred to use beforehand the textiles substrate with a surface treatment which performed introductory processing of an anionic machine or a cationic machine for a fiber surface. The complex formation mentioned above also between aluminum ion or poly aluminum ion will be made, and this will be considered because bigger electrostatic associative strength is acquired, if an anionic machine exists in the fiber surface of textiles substrate 1. When a cationic machine exists in the fiber surface of textiles substrate 1, when a textiles substrate is given to solution of aqueous aluminum compounds, such as alum solution, it is, for example, A fiber surface is adsorbed in the negative ion of the aqueous aluminum compound origin in the solution (for example, sulfuric acid ion), the negative ion is replaced by a hydroxyl group in a subsequent flush process, and a phosphoric acid zirconium layer is considered because it adsorbs firmly by the fiber surface after the substitution.

0032As an anionic machine, a hydroxyl group, a carboxyl group, a phosphate group, etc. are mentioned, and if it is a method by which Texture of a textiles substrate is not spoiled as an introducing method, the publicly known method known for the processing field of textiles can be used without restriction, for example. For example, to natural system textiles, such as a cellulosic fiber and protein system textiles, there are the method of generating oxidized cellulose using nitrogen peroxide or nitrogen dioxide, a method of generating the oxidized cellulose by an ultraviolet exposure, the method of etherifying carboxylic acid using a catalyst, etc.

0033When introducing especially a carboxyl group, a phosphate group, etc., since a carboxyl group, a phosphate group, etc. can be certainly introduced to various kinds of textiles, the graft polymerization method of the vinyl monomer containing the carboxyl group by electron irradiation, a phosphate group, etc. is preferred. The method can carry out the graft polymerization of the vinyl monomer with the front glaring method make vinyl monomer solution contact, or the coincidence irradiation method which makes a textiles substrate and a vinyl monomer live together, and irradiates with an electron beam, after irradiating a textiles substrate with an electron beam. As a carboxyl group content vinyl monomer, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, a maleic acid anhydride, an itaconic anhydride, a methacrylic acid anhydride, etc. are mentioned, for example. These may use one sort independently, and may mix and use two or more sorts. As a phosphate group content vinyl monomer, For example, mono-(2-methacryloiloxy-ethyl)acid phosphate, The (2-methacryloiloxy-ethyl) acid phosphate, mono-(2-acryloyloxyethyl)acid phosphate, The (2-acryloyloxyethyl) acid phosphate, etc. are mentioned. These may use one sort independently, and may mix and use two or more sorts.

0034It is preferred to use a vinyl monomer as solution and to use it on the occasion of the graft polymerization of a vinyl monomer, and the solvent used for manufacture of the solution in that case (vinyl monomer solution) can mention organic solvents other than water, such as alcohols and ethylene dichloride, for example, although restriction in particular is not carried out. As for the concentration of vinyl monomer solution, it is preferred that it is 5 to 50 % of the weight, and it is more preferred that it is 5 to 20 % of the weight. Although there is no restriction in particular in the dose of the electron beam with which a textiles substrate is irradiated, about 10-100 kGy is preferred. When there is a possibility that graft polymerization may not fully be performed as the dose of an electron beam is less than 10 kGy and the dose of an electron beam exceeds 100kGy, there is a possibility of degrading textiles. Although restriction in particular does not have accelerating voltage, either and it can be suitably chosen with the thickness etc. of the textiles substrate to process, it is usually about 100-300 kV. As for electron irradiation atmosphere, it is preferred that oxygen concentration is low, and it is preferred. [ of especially the thing to perform under a nitrogen atmosphere ]

0035As for the rate of a graft of the monomer in graft polymerization, about 1 to 20 % of the weight is preferred, and its about 5 to 10 % of the weight is more preferred. If the rate of a graft serves as the tendency for aluminum ion, poly aluminum ion, or the amount of adhesion of phosphoric acid zirconium to fall, in less than 1 % of the weight and exceeds 20 % of the weight, it will become the tendency for original Texture which a textiles substrate has to fall. "The rate of a graft" in this specification refers to the rate of a weight part of the monomer to the textiles substrate before a graft polymerization reaction which carried out the graft, and it asks with a following formula.

0036The rate of a graft (% of the weight) = [(dry weight of textiles substrate in front of dry weight-graft polymerization of textiles substrate after graft polymerization) dry weight of textiles substrate in front of /graft polymerization] x100

0037When introducing a hydroxyl group into the surface of protein system textiles, such as animal hairs, such as wool, cashmere, and Angora, the method to which the polyphenol which has three or more hydroxyl groups is made to react is preferred in one molecule, such as tannin, tannic acid, a 5 time child, Gallic, and gallic acid. This method can be performed by immersing a textiles substrate in 1 - 100mM solution (temperature: about 10-100 ) of polyphenol for about 0.25 to 2 hours, for example. As for the amount of reactions of polyphenol, about 1 to 50 % of the weight is preferred to a textiles substrate. In less than 0.1 % of the weight, if the effect of introducing a hydroxyl group may not fully be acquired and exceeds 50 % of the weight, it will become difficult for unevenness to arise in adsorption or to remove ion excessive at the time of washing, and it will become the tendency for the intensity of a lamination film to fall.

0038The method of a quarternary-ammonium-salt machine, an amino group, the 4th class phosphonium machine, etc. being mentioned, and performing the graft polymerization by above-mentioned electron irradiation as these introducing methods as a cationic machine, using the vinyl monomer containing this cationic machine, for example is preferred. A cationic machine has a preferred quarternary-ammonium-salt machine, and quarternary ammonium salt of dialkylamino Alkyl (meta) acrylate is preferred for it as a vinyl monomer containing a quarternary-ammonium-salt machine. A Alkyl machine means a with a carbon number of three or less thing here. The classic example of dialkylamino Alkyl (meta) acrylate is dimethylaminoethyl (meta) acrylate. The range above-mentioned [ the reaction conditions in a graft polymerization reaction, the rate of a graft, etc. ] is followed.

0039[Photocatalyst]<br />A photocatalyst used by the present invention is a metal oxide which can excite by light irradiation (especially ultraviolet exposure), can demonstrate oxidation reduction capability, and can disassemble an organic matter. Specifically, an oxide of transition metals, such as titanium oxide (titanium dioxide), titanic acid, titanic acid salts, niobic acid, niobic acid, Titano niobic acid, a zinc oxide, and copper oxide, etc. are illustrated. Especially, what is preferably titanium oxide and is in a titanium dioxide or a low orderer oxidation state from the point of having high photocatalyst activity is good. Although the thing of various crystal types, such as an anatase, a rutile type, and a brookite type, can be used for titanium oxide, its anatase is preferred especially. In the present invention, as a photocatalyst (metal oxide), it is preferred that the mean particle size of a primary particle is less than (namely, nano level) 1 micrometer, especially crystallinity is high and the mean particle size of a primary particle is preferred at the point that a thing of 50 nm or less has high photocatalyst activity. Although limitation in particular is not carried out, since the minimum of the mean particle size of the primary particle of a photocatalyst (metal oxide) has a possibility that a band gap may spread by a quantum size effect, it may become impossible to use a near-ultraviolet light effectively, and reaction efficiency may fall when it is too small, its 20 nm or more is preferred. "The mean particle size of a primary particle" here is the average value which asked for the diameter of a particle from the picture under the electron-microscopic-picture observation depended on the FE-SEM(electric field radiation scanning electron microscope):Hitachi type S-4500. The photocatalyst (metal oxide) below 1 micrometer tends to condense [ tend ] the mean particle size of a primary particle, and it is usually fixed to a phosphoric acid zirconium layer in the state of secondary particles (adsorption).

0040In the textiles of the present invention, photocatalyst 3 is electrostatically fixed to phosphoric acid zirconium layer 2 (phosphoric acid zirconium layer 2b of the outermost layer of phosphoric acid zirconium multiplex layer 10). That is, many are just charged in an acidic solution according to the dissociation balance of hydrophilic functional groups, such as a surface hydroxyl group, and metal oxides, such as titanium oxide used as photocatalyst 3, are negatively charged in an alkaline solution. Photocatalyst (metal oxide) 3 just electrified underwater is made to stick to phosphoric acid zirconium layer 2 (2b) charged negatively electrostatically, and photocatalyst 3 is made to fix to the outermost part of a textiles substrate in the present invention, so that the electrification tendency of a metal oxide underwater [ this ] may be used and mentioned below. Under the present circumstances, the phosphate group looked at by the partial structure of phosphoric acid zirconium, It has the character which carries out a covalent bond specifically to metal oxides, such as titanium oxide, and 4.1 densities/square of phosphoric acid structure of phosphoric acid zirconium are nm(s) at the same time it carries out proton dissociation and is tinged with a lasting minus electric charge of a phosphoric acid zirconium layer. Since it exists very with high density, even if it is a nanoparticle-like metal oxide, it becomes possible to fix firmly by many point electrostatic bond and a specific covalent bond.

0041As above-mentioned, the photocatalyst below 1 micrometer tends to condense [ tend ] the mean particle size of a primary particle, and it is usually fixed in the state of secondary particles (adsorption). Since this photocatalyst particle is adsorbed in general as a single particle layer, the thickness of a photocatalyst layer serves as a thin layer of 1 micrometer or less. However, there is a tendency condensed strongly in a transverse direction on the surface of a product, and if surface observation is carried out in SEM, several microns condensation structure will be observed. The diameter of a particle of the viewpoints of the support stability to phosphoric acid zirconium layer 2 (2b), Texture maintenance of textiles, etc. to secondary particles has the preferred range of 50-5000 nm, and its range of 1000-3000 nm (1-3 micrometers) is more preferred. The secondary particles of a photocatalyst are formed in the water dispersion of the photocatalyst for making phosphoric acid zirconium layer 2 (2b) support a photocatalyst, and form the particles of 2-20 micrometers of mean particle sizes. However, since a particle with a size of 5 micrometers or more is easily removed by water washing after support, it forms a with about 1 micrometer in thickness, and a condensation size [ of a transverse direction ] of about 1-3 micrometers secondary particle in the surface of phosphoric acid zirconium layer 2 (2b). The diameter of a particle of the underwater dispersed photocatalyst is measured by the light scattering method in the inside of the water dispersion of the photocatalyst concerned. The diameter change of a particle between the secondary particles in the water dispersion of a photocatalyst and the secondary particles supported by the phosphoric acid zirconium layer is small, and the diameter of a particle of the secondary particles in the inside of the water dispersion of a photocatalyst is reflected in the diameter of a particle of the photocatalyst supported by the phosphoric acid zirconium layer as it is.

0042In the textiles of the present invention, limitation in particular is not carried out but, as for the amount of support of photocatalyst 20, the simple grain child adsorption film or secondary particle adsorption film of the photocatalyst should just be formed in the surface of phosphoric acid zirconium layer 2 (2b). In the present invention, since a photocatalyst meets in the photocatalyst dispersion liquid used for manufacture, secondary particles are formed and it sticks to phosphoric acid zirconium layer 2 (2b) electrostatically, the secondary particle adsorption film of a photocatalyst is formed easily. here -- "a simple grain child adsorption film" -- the surface of phosphoric acid zirconium layer 2 (2b) -- the primary particle of a photocatalyst -- abbreviated -- it is in the state where it is adsorbing by uniform density (adhesion) -- "a secondary particle adsorption film", The primary particle which the photocatalyst adsorbed as secondary particles or held the single particle layer is in the state which carried out surface condensation. in addition -- the surface of phosphoric acid zirconium layer 2 (2b) does not necessarily need to be completely covered with the particles of the photocatalyst -- the surface of phosphoric acid zirconium layer 2 (2b) -- 30% or more should just be covered in general with photocatalyst particles. That is, 30% or more is preferred, and more preferably is 60% or more, and the covering rate by the photocatalyst in the surface of phosphoric acid zirconium layer 2 (2b) is 80% or more especially preferably. Since it will become unstable on the contrary adhering to the phosphoric acid zirconium layer of a photocatalyst, especially it will become the tendency to become easy to exfoliate underwater if adsorption support of the photocatalyst is superfluously carried out on the surface of phosphoric acid zirconium layer 2 (2b), it is not desirable. The above-mentioned covering rate is computable from the picture of scanning electron microscope photographs, such as FE-SEM.

0043[A process of the textiles which supported the photocatalyst]<br />(1) Production of a textiles substrate-phosphoric acid zirconium layer compound thing<br />(a) when manufacturing the textiles of the mode shown in Drawings 1 and 2, after immersing a textiles substrate in solution of an aqueous aluminum compound and washing it -- or It dries, after immersing a textiles substrate in phosphoric acid zirconium monolayer exfoliation dispersion liquid and washing it, without doing the immersion to solution of this aqueous aluminum compound, and flush work, The compound thing which the phosphoric acid zirconium layer united with the textiles substrate via direct or aluminum ion or poly aluminum ion is produced.

0044(b) When the textiles of the mode shown in Drawing 3 are manufactured, A textiles substrate is immersed in solution of an aqueous aluminum compound, and the 2nd work is done twice [ at least ] or more in the 1st work to wash and the 2nd work that immerses a textiles substrate in phosphoric acid zirconium monolayer exfoliation dispersion liquid, and washes it, The textiles substrate repeatedly processed by turns so that the 2nd work might turn into the last work is dried, and the compound thing which the phosphoric acid zirconium multiplex layer containing the phosphoric acid zirconium layer more than two-layer united with the textiles substrate via aluminum ion or poly aluminum ion is produced.

0045Generally, the concentration of solution of an aqueous aluminum compound is about 0.1-200 mM. If there is more concentration than 200mM, homogeneous adsorption becomes difficult, and since the amount of adsorption and an adsorption rate fall, by less than 0.1 mM both, it will become a tendency with insufficient covering. Generally, the concentration (phosphoric acid zirconium content) of the phosphoric acid zirconium monolayer exfoliation dispersion liquid used for formation of a phosphoric acid zirconium layer is 1 mg - about 1 g/L, preferably 0.1g - about 1 g/L. If there is more concentration of phosphoric acid zirconium monolayer exfoliation dispersion liquid than 1 g/L, there will be a tendency gelled for Thixotropy and it will become a tendency in which less than 1 mg/L of covering is insufficient.

0046That which is performed under the environment which the dryness performed after being immersed to the phosphoric acid zirconium monolayer exfoliation dispersion liquid of a textiles substrate is processing neglected for about 12 to 24 hours under the environment of the temperature of about 5-30 and 20 to 80% of humidity, and interrupted sunlight (shade-drying) is preferred. This time can be shortened by drying operation by centrifugal drying etc.

0047(2) Support of a photocatalyst<br />First, photocatalysts, such as a ball for pulverization of a zirconia ball etc. and titanium oxide, and distilled water are put into the ball mill which used the planet stirrer etc., for example, uses a zirconia ball etc. as a ball for pulverization, and it is 300-1000 rpm, The work which adds and agitates distilled water after churning for a predetermined period (generally about 15 to 120 minutes) is repeated, and photocatalyst content prepares the paste which is 100 g/L. Next, the water dispersion which added a proper quantity of the above-mentioned photocatalyst pastes to the acid water which added chloride etc. to distilled water and adjusted pH to three to about 5.5, was distributed, and the photocatalyst was charged right and distributed is prepared. As for the content of the photocatalyst in the dispersion liquid, about 0.05-5 g/L is preferred. If there is more concentration (content) of a photocatalyst than 5 g/L, while becoming easy to exfoliate, it will become a tendency of a yield fall, and will become the tendency that support sufficient in less than 0.05 g/L cannot be performed. Next, natural seasoning is washed and carried out after the textiles substrate-phosphoric acid zirconium layer compound thing produced above (1) is immersed into the water dispersion of the photocatalyst to apply. And it sinters at 60-150 after dryness for about 1 to 3 hours. That which is performed under the environment which natural seasoning here is processing neglected for about 12 to 24 hours under the environment of the temperature of about 15-30 and 20 to 80% of humidity, and interrupted sunlight (shade-drying) is preferred. This time can be shortened by drying operation by centrifugal drying etc. The textiles which supported the photocatalyst for the photocatalyst to have stuck to the phosphoric acid zirconium layer of the outermost layer electrostatically by sintering, and to have been fixed are obtained.

0048The textiles which supported the photocatalyst of the present invention are clothing, bedding, and a tablecloth, It is suitably [ for the textiles of various uses, such as interior equipments, such as wallpaper, a curtain a carpet, a sheet, and a chair, ] applicable, Especially, in the textiles which supported the conventional photocatalyst that Texture of textiles was not spoiled, since the subject were difficult for the improvement is cancelable, it can be conveniently used as an object for the cloth of various clothing regardless of an underwear, underwear, and a coat. the case where it wears as clothes since it has photocatalyst activity by irradiating the photo catalyst fiber of the present invention with the weak ultraviolet rays by sunlight or an interior light -- or When it is used as wallpaper, a sheet, a cover, etc., only the surface coat by which light irradiation is carried out is activated, and the back with which it is not irradiated with light does not show activity.<br />It is used as a white pigment for many years, and resources are also enough, on the other hand, titanium oxide is comparatively safe also for phosphoric acid zirconium, and there is also little health disturbance. Alum is also approved as food additives, such as pickles, and it is thought that the danger for a human body is very small.

<p num="0049">Hereinafter, although an example and a comparative example are shown and the present invention is explained more concretely, the present invention is not limited to the following example.<br />[1] Use material<br />1. Textiles Substrate<br />100% of cotton plain weave mercerized cotton going-up cloth (unsettled article) and a total of five kinds of cloth of the following of a processing treatment article which performed various processing treatment were prepared.<br />Cloth 1: Dimethylamino ethyl acrylate quarternary-ammonium-salt processing article<br />Cloth 2: Mono-methacryloiloxy-ethyl phosphate processing article<br />Cloth 3: Acrylic acid processing article<br />Cloth 4: Gallic acid processing article<br />Cloth 5: Unsettled article</p><p num="0050">*1) Dimethylamino ethyl acrylate quarternary-ammonium-salt processing : as opposed to one field of 100% of cotton plain weave mercerized cotton going-up cloth, 20kGy irradiation of the electron beam was carried out under a nitrogen atmosphere by electro curtain type electron beam irradiation device EC250/15 / 180L (product made from Eye Electron Beam). The cloth which carried out electron irradiation was immersed in solution of dimethylamino ethyl acrylate quarternary ammonium salt 10%, and it extracted becoming about 70% of the weight of an impregnating rate to cloth with mangle, and carried out maturation treatment at 35 for 18 hours. 20kGy irradiation of the electron beam was again carried out under a nitrogen atmosphere to another [ with which it did not irradiate ] field by electro curtain type electron beam irradiation device EC250/15 / 180L (Eye Electron Beam). Maturation treatment was carried out at 35 after irradiation for 2 hours. Subsequently, it washed in order to remove an unreacted medicine, and it dried. The rate of a graft was 2.0%.</p><p num="0051">*2) Mono-methacryloiloxy-ethyl phosphate processing : same processing was carried out except having used mono-methacryloiloxy-ethyl phosphate for the medicine in *1. The rate of a graft was 4.2%.</p><p num="0052">*3) Acrylic acid processing : same processing was carried out except having used acrylic acid for the medicine in *1. The rate of a graft was 7.4%.</p><p num="0053">*4) Gallic acid processing : it dried by a 100 hot wind after 2-hour immersion in 10mM solution of gallic acid.</p><p num="0054">2. Ethanol<br />3. Solution of Potassium Alum (Concentration: 30mM)<br />4. Phosphoric Acid Zirconium Monolayer Exfoliation Dispersion Liquid (Concentration: 1mM)<br />* Phosphoric acid zirconium (alpha-Zr (HPO))_４）_２2H_２O) The water of 20mL was made to distribute 0.15 g by shake, after carrying out ionic exchange by tetrabutylammonium solution (alkaline chemicals) 10%, it centrifuged, and what diluted the supernatant fluid 40 times with water was used.<br />5. Titanium Oxide (Brand Name UFA by Showa Titanium Incorporated Company) : Ring Shape Ultrafine Particle Anatase Titanium Oxide</p><p num="0055">[2] Photocatalyst processing<br />A. Production of a textiles substrate-phosphoric acid zirconium multiplex layer compound thing<br />(1) Make cloth immersed in ethanol and wash it for 24 hours.<br />(2) Wash with distilled water and remove a part for ethanol.<br />(3) Cloth is immersed in solution of potassium alum for 15 minutes.<br />(4) Wash twice in distilled water and dry under the atmosphere in a dark place.<br />(5) Cloth is immersed in phosphoric acid zirconium monolayer exfoliation dispersion liquid for 15 minutes.<br />(6) Wash twice in distilled water.<br />(7) (3) - (6) is repeated further 4 times, and a five-layer phosphoric acid zirconium layer is formed.<br />The textiles substrate to which the phosphoric acid zirconium multiplex layer which has a five-layer phosphoric acid zirconium layer after the work of (8) and (7) stuck is shade-dried.</p><p num="0056">B. Production of a textiles substrate-phosphoric acid zirconium multiplex layer-titanium oxide (layer) compound thing<br />(1) Manufacture of a titanium oxide paste<br />A planet stirrer is used. 9 g of zirconia balls (2 mm in diameter), titanium oxide 2g, and distilled water 4mL are put into a zirconia ball mill. Weight is adjusted with a zirconia ball and water so that the weight of one of the two's ball mill may also already become the same. It agitates at 450 rpm for 15 minutes. If churning finishes, distilled water will be added 4 mL and it will agitate on the conditions. Distilled water is put in, churning is repeated and a 100-g/L paste is completed in the place where distilled water became 20mL.<br />(2) Manufacture of a titanium oxide water dispersion<br />The distilled water of 300mL is adjusted the pH to 4.5 with chloride, 3mL distribution of the titanium oxide paste of (1) is carried out into the solution, and 1 g/L of titanium oxide distribution solution is prepared.<br />(3) The textiles substrate-phosphoric acid zirconium multiplex layer compound thing produced by above-mentioned A. is immersed in the titanium oxide distribution solution of (2) for 15 minutes, and wash once with distilled water.<br />When shade-drying the compound thing after the work of (4) and (3) and drying, it is made to sinter at 120 for 2 hours.</p><p num="0057">Example 1<br />The above-mentioned photocatalyst processing was given to cloth 1 (dimethylamino ethyl acrylate quarternary-ammonium-salt processing article).</p><p num="0058">Example 2<br />The above-mentioned photocatalyst processing was given to cloth 2 (mono-methacryloiloxy-ethyl phosphate processing article).</p><p num="0059">Example 3<br />The above-mentioned photocatalyst processing was given to cloth 3 (acrylic acid processing article).</p><p num="0060">Example 4<br />The above-mentioned photocatalyst processing was given to cloth 4 (gallic acid processing article).</p><p num="0061">Comparative example 1<br />Cloth 5 (unsettled article) was used as it was.</p><p num="0062">The aluminum ion or poly aluminum ion which stuck to cloth in Examples 1-4 is about 62 microg/m, respectively.^２It came out. Also in any of Examples 1-4, the thickness of about 5 nm and a phosphoric acid zirconium layer (much more) of the whole phosphoric acid zirconium multiplex layer thickness was about 0.7 nm. The thickness of the aluminum ionized layer (much more) was about 0.3 nm. Here, the thickness of the whole phosphoric acid zirconium multiplex layer is FE-SEM(electric field radiation scanning electron microscope):Hitachi, Ltd. Make. S-4500 type It is the value judged from the picture photograph of the obtained compound thing section.</p><p num="0063">Also in any of Examples 1-4, the diameter range of a particle of the primary particle of the titanium oxide fixed to the phosphoric acid zirconium layer of the outermost layer (adsorption) is 5-10 nm (mean particle size: 8 nm), The diameter range of a particle of the secondary particles which this primary particle condensed was 50-300 nm (mean particle size: 100 nm).</p><p num="0064">A diameter of a particle of a primary particle of titanium oxide particles is FE-SEM(electric field radiation scanning electron microscope):Hitachi, Ltd. Make. S-4500 type It is a calculated value from a picture photograph of an acquired fiber surface. A mean particle size is the average value of two or more diameters of a particle. Magnification is set up and, specifically, an electron microscopic picture is taken so that 500 or more particles may go into a view first, Next, the area of the image of each particle in a photograph was computed, the diameter (namely, diameter of Haywood) of the circle which has the area from this computed area further was computed to make the diameter of a particle of each particle, the number average of the measurement number was calculated, and it was considered as average particle diameter.</p><p num="0065">The diameter of a particle of secondary particles (mean particle size) was measured with the light scattering particle-size-distribution plan (Shimadzu: SALD-200V) about the particles in the sample solution (pH:5) which diluted the titanium oxide water dispersion with water. Average particle diameter is a diameter of an arithmetic average.</p><p num="0066">(1) Deodorization examination 1<br />The following examinations A and B were done per Examples 1-3 and comparative example 1. The irradiation conditions of the black light set irradiation intensity to 1.0 mW. The examination followed the cloth after 10 times operation in the wash examination based on the test method indicated to the cloth before wash, and appended chart 1 (number 103) of JIS L0217:1995.</p><p num="0067">Examination A (aldehyde)<br />1 g of samples were put into the tedlar bag of 1L, the predetermined concentration (18.0 ppm) injection of the acetaldehyde was carried out, and it irradiated with the black light, and measured the residual gas concentration of 2 hours and 24 hours after with the detecting tube. The deodorization rate computed the sample based on the following formulas on the basis of the concentration (blank test concentration) measured in the state where it cannot enter.<br />Deodorization rate (%) =(blank test concentration-sample examination concentration) (/(blank test concentration)) x100</p><p num="0068">Examination B (hydrogen sulfide)<br />1 g of samples were put into the tedlar bag of 1L, the predetermined concentration (20.0 ppm) injection of the hydrogen sulfide was carried out, and it irradiated with the black light, and measured the residual gas concentration of 2 hours and 24 hours after with the detecting tube. The deodorization rate was computed on the basis of blank test concentration like examination A.</p><p num="0069">(2) Deodorization examination 2<br />The following examinations A and B were done per Example 4 and comparative example 1. The examination followed the cloth after 10 times operation in the wash examination based on the test method indicated to the cloth before wash, and appended chart 1 (number 103) of JIS L0217:1995.</p><p num="0070">Examination A (aldehyde)<br />It carried out like examination A of deodorization examination 1 except having changed the predetermined concentration of acetaldehyde into 16.0 ppm.</p><p num="0071">Examination B (hydrogen sulfide)<br />It carried out like examination B of deodorization examination 1 except having changed the predetermined concentration of hydrogen sulfide into 32.0 ppm.</p><p num="0072">The result of deodorization examinations 1 and 2 is shown in Table 1 and 2.</p><p num="0073"><tables num="1"><img file="WO2010092999A1_D0001.tif" /></tables></p><p num="0074"><tables num="2"><img file="WO2010092999A1_D0002.tif" /></tables></p><p num="0075">(3) Ultimate analysis<br />Half-quantitative elemental analysis by the fluorescence X line analysis wash before and after wash was carried out about each cloth of Examples 1-4 and comparative example 1.<br />Wavelength-dispersion type fluorescence X-rays spectroscopic analyzer: ZSX 100e (Made by Rigaku)<br />Measurement conditions: The sample was pierced to 30 mmphi and carried out the time base range in B-U by the EZ scanning method under a vacuum atmosphere.<br />A result is shown in Table 3. The unit of the numerical value in front is mass %.</p><p num="0076"><tables num="3"><img file="WO2010092999A1_D0003.tif" /></tables></p><p num="0077">As shown in Tables 1 and 2, clear odor eliminating was accepted under light irradiation in the cloth to which photocatalyst processing of Examples 1-4 was given. It turned out that after wash has the endurance which the odor eliminating maintains. After wash has checked that quantity support of the photocatalyst was carried out enough from the result (Table 3) depended on fluorescence X line analysis.</p><p num="0078">(4) Texture of cloth<br />In the tactile feeling examination according [ Texture of Examples 1-4 (photocatalyst processed goods) ] to organic functions, the difference almost became as compared with comparative example 1 (raw article). It has checked there being almost no difference in results, such as viewing and a sense-of-color inspection, with comparative example 1 (raw article), and almost not affecting Texture of a textiles substrate by photocatalyst processing.</p>

0079Since the protective film and the photocatalyst film are laminated, without spoiling Texture of a textiles substrate, even daily necessaries, such as clothes, an umbrella and a bag, and a carpet besides housing interiors, such as a curtain and wallpaper, are large, and the textiles which supported the photocatalyst of the present invention are applicable. According to the protection effect by firm phosphoric acid Zirconium, while being able to use as ultraviolet-rays cut textiles, it is expectable in ultraviolet rays also as a protective film of weak Aramid, polyamide, and nylon system textiles.

00801 Textiles Substrate<br />2 Phosphoric Acid Zirconium Layer<br />3 Photocatalyst<br />4 Aluminum Ion or Poly Aluminum Ion<br />10 Phosphoric Acid Zirconium Multiplex Layer

0081This application is based on application for patent 2009-31931 for which it applied in Japan, and the contents are altogether included in this specification.