WO2007116302A2

WO2007116302A2 - Semifinished products, footwear elements, apparatuses and methods for obtaining footwear elements, and footwear

Info

Publication number: WO2007116302A2
Application number: PCT/IB2007/000935
Authority: WO
Inventors: Luigino Gravelli; Ambrogio Della Valle Renato
Original assignee: Nm Tech Nanomaterials Microdevice Technology Ltd.
Priority date: 2006-04-11
Filing date: 2007-04-11
Publication date: 2007-10-18
Also published as: ITMO20060121A1; WO2007116302A3

Abstract

Semifinished products comprise footwear elements and/or materials suitable for being used to obtain footwear elements, a support made of a desired material and are characterised in that they comprise layer means (200, 201, 202) having photocatalytic functions arranged on said semifinished products; footwear means comprises footwear elements, and is characterised in that it comprises layer means (200, 201, 202) having photocatalytic functions arranged on said footwear elements; an apparatus for treating semifinished products (2) comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprises moving means (3, 4; 3, 4' ) for moving along a desired path (F) said semifinished products (2) and is characterised in that it comprises applying means (8, 10, 11, 12, 13; 8, 50) arranged along said path (F) for applying a solution (200, 201, 202) of a photocatalytic material to said semifinished products (2) .

Description

Semifinished products , footwear elements , apparatuses and methods for obtaining footwear elements, and footwear

The invention relates to semifinished products comprising footwear elements and/or materials for making footwear elements and/or improved footwear, apparatuses and methods for obtaining improved footwear, and footwear elements, such as for example arch-supports, foot-straps, vampers, soles, heel-supports, etc.

In particular, the invention relates to footwear elements and footwear having antibacterial, antimicrobial and antifungal properties.

Footwear is a product that is necessary and indispensable for everyone, and different types of footwear exist that adapt to the different needs and/or tastes of the users. Using footwear is often associated with the creation of bad smells, especially when a given type of footwear is used continuously for a prolonged period, or in particular conditions of use, or also in particular environmental conditions .

Such bad smells, which are caused by the sweating of the feet due to the contact between the foot and the shoe, in particular in the zone of the arch, cause discomfort to the user and may compromise subsequent use of the footwear. Often, in order to limit the drawback of bad smell, the footwear is washed very frequently.

This solution is only momentaneous because with further use of the footwear the drawback returns, further this solution cannot be adopted with all types of footwear and above all this solution causes great wear to the footwear, which has to be replaced very frequently.

In order to attempt to overcome such drawbacks, in various patents, which are mainly filed in the name of "Geox", including for example EP 1 201 143, footwear is provided with holes for venting the sweat that is created due to the use of the footwear. Nevertheless, this type of footwear does not enable fungi and/or bacteria that may be generated inside the footwear following use thereof to be eliminated.

Further, the teachings of EP 1 201 143 cannot be applied to all types of footwear and thus have a limited effect.

An object of the invention is to make improved footwear, and/or footwear elements that do not have the drawback of creating bad smells even when a user uses them for a long period and make successive and continuous uses thereof.

Still another object is to provide footwear, and/or footwear elements that ensure elevated hygiene conditions for a user.

Still another object is to provide footwear and/or footwear elements having antifungal, antibacterial properties.

A further object is to provide footwear, and/or footwear elements that enable the proliferation of microorganisms to be prevented and bacteria and viruses to be eliminated that physiologically may form due to the use of the footwear.

A still further object is of footwear, and/or footwear elements, the antibacterial, antifungal, odour-eating properties of which are not impaired and/or which can be regenerated by simple washing the footwear, and/or the footwear elements with water.

Still another object is to provide apparatuses and methods for producing semifinished products comprising footwear elements and/or materials for making footwear elements and/or improved footwear.

In a first aspect semifinished products are provided, comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprising a support made of a desired material and characterised in that they comprise layer means having photocatalytic functions arranged on said semifinished products.

Preferably, said layer means is provided on a surface of said semifinished products suitable for coming into contact in use with a user of said semifinished products and/or of said footwear elements. In an embodiment, said photocatalytic layer means comprises

Titanium dioxide, preferably in the form of Anatase, and/or modified peroxytitanic acid.

In another embodiment, said semifinished products further comprise further Titanium dioxide layer means in the form of

Rutile, interposed between a surface of said semifinished products and said layer means.

The further layer means enables the semifinished products to be protected from possible chemical attacks and promotes the adhesion of the layer means to the semifinished products.

In a further embodiment said semifinished products further comprise still further layer means, in Titanium dioxide as peroxytitanic acid, or in other compounds having a strong adhesive force and which are not oxidizable, interposed between a surface of said semifinished products and said layer means, and/or said further layer means if provided.

Said still further layer means may comprise a silicon based or peroxytitanic acid-based primer, the further layer means protecting said semifinished products.

In a second aspect of the invention footwear means is provided comprising footwear elements, characterised in that they comprise layer means having photocatalytic functions arranged on said footwear elements.

In a third aspect of the invention there is provided an apparatus for treating semifinished products comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprising moving means for moving along a desired path said semifinished products and characterised in that it comprises applying means arranged along said path for applying a solution of a photocatalytic material to said semifinished products.

In an embodiment, said apparatus further comprises heating means arranged along said path and suitable for heating said solution to make the excess solvent thereof evaporate.

In another embodiment, said applying means and said heating means respectively comprise a plurality of applying means and a plurality of heating means arranged in an alternating manner along said path.

In this way, it is possible to apply the photocatalytic layer means to the semifinished products repeatedly through successive applications, each one of which applications is followed by heating the semifinished products with the heating means for making the excess solvent evaporate, promoting the homogeneity of the layer means on the semifinished products and the activation of the particles of the photocatalyst of the layer means.

In a further embodiment said applying means comprises containing means arranged for containing a solution of a photocatalytic material and immersion means for immersing said semifinished products in said solution.

Tensioning means can be further provided for maintaining said footwear elements in tension during immersion in said containing means .

In an embodiment, heating means is provided placed upstream of said containing means and arranged for heating said semifinished products before immersing the semifinished products in said solution.

In another embodiment, there is provided further heating means, placed downstream of said containing means and arranged for heating said semifinished products for making the excess solvent of said solution evaporate.

In a fourth aspect of the invention there is provided a method for treating semifinished products comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprising moving said semifinished products along a desired path and applying a solution of a photocatalytic material to said semifinished products during said moving.

In an embodiment, heating said solution for making the excess solvent evaporate during said moving is provided. In another embodiment, during said moving, repeating said applying and said heating in an alternating manner is provided.

In some embodiments, said method comprises covering said semifinished products with a silicon based or a peroxytitanic acid-based primer before applying said photocatalytic material solution.

A further embodiment provides accumulating a desired quantity of a solution of a photocatalytic material in containing means provided along said path and immersing said semifinished products in said solution.

Tensioning said semifinished products during said moving can also be provided.

In an embodiment, heating said semifinished products before said immersing in said solution is provided.

In another embodiment, there is further provided heating said semifinished products after said immersing for making the excess solvent of said solution evaporate.

In some embodiments applying to said semifinished products a silicon based or a peroxytitanic acid-based primer is provided before immersing said semifinished products in said photocatalytic solution.

In an embodiment said semifinished products comprise footwear, and/or footwear elements.

In a fifth aspect of the invention, footwear means is provided comprising footwear elements provided with photocatalytic layer means.

In a sixth aspect of the invention there is provided the use of Titanium dioxide for treating semifinished products comprising footwear and/or footwear elements and/or materials suitable for being used to obtain footwear elements, in such a way as to obtain semifinished products having photocatalytic properties.

In an embodiment, there is provided using a liquid colloidal solution of modified Anatase peroxide and/or peroxytitanic acid in water. Owing to the invention, it is possible to make semifinished products comprising footwear elements and/or materials suitable for being used to obtain footwear elements and/or footwear, footwear and/or footwear elements having antifungal, antibacterial properties and which also prevent the creation of bad smells.

In an embodiment said layer means, and/or said further layer means, and/or said still further layer means comprise Titanium dioxide in the form of Brookite, and/or other compounds having strong adhesive power.

In another embodiment said layer means, and/or said further layer means, and/or said still further layer means comprise surfactants and/or other additives that are added to the mixtures of Titanium dioxide compounds.

These additives can be in the form of powder, in the form of microspheres, in a laminar form, or in any other form that is suitable for mixing said additives with Titanium-based compounds, forming, for example, a solution in suitable solvents .

These additives can be used separately or aggregated with silicon, colloidal silicon, or other materials that are suitable for gripping.

These additives comprise silver (Ag) compounds and/or a derivative thereof, preferably a silver salt such as, for example, silver acetate (CH₃COOAg) . The silver compounds, if they are present, generally have a concentration comprised between approximately 0.001% and approximately 0.5% in total weight of the prepared mixture. The CH₃COOAg, if it is present, generally has a percentage comprised between approximately 0.005% and approximately 0.1% in total weight of the prepared mixture.

The additives may further comprise copper (Cu) , and/or a derivative thereof, and/or copper-based compounds, preferably cupric oxide (CuO) or a copper salt (II), such as, for example, CuSO₄. The copper compounds, if they are present, will have a concentration comprised between B2007/000935

approximately 0.001% and approximately 0.5% in total weight of the prepared mixture, preferably between approximately 0.005% and approximately 0.1% by weight.

It has been seen that the presence of silver or derivates thereof, and/or of copper, and/or of one or more copper (II) salts in the Titanium based suspensions enables surprising antibacterial properties to be given to suitable materials to which the obtained suspensions are applied, even in the absence of luminous irradiation, as will be explained better in the followings in the present invention.

The mixtures may further comprise one or more substances with a surfactant action, preferably in a weighted concentration comprised between approximately 0.001% and approximately 5% in total weight of the prepared mixture. The mixtures may further comprise, silicon (SiO₂) , preferably in colloidal form and present in a concentration comprised between approximately 0.5% and approximately 2.0% in total weight of the prepared mixture.

In a further embodiment, said semifinished products comprising footwear elements and/or materials suitable for being used to obtain footwear elements and/or footwear, further comprise at least a component chosen between sodium hydroxide (NaOH) , lithium oxide (Li₂O) , sodium sulphite heptahydrate (Na₂S₂O₃ ⁴TH₂O), sodium thiosulphate pentahydrate (Na₂SO₃* 5H₂O) , and/or silicon (SiO₂).

The sodium hydroxide is preferably present with a weighted concentrations comprised between approximately 0.01% and approximately 0.1% in total weight of the prepared mixture; the lithium oxide Li₂O is preferably present in a concentration comprised between approximately 0.01% and approximately 1.0% in total weight of the prepared mixture. The sodium sulphite heptahydrate Na₂SO₃* 7H₂O is preferably present in concentrations comprised between approximately 0.01% and approximately 0.1% by weight, the sodium thiosulphate pentahydrate Na₂S₂O₃'5H₂O, preferably in concentrations comprised between approximately 0.001% and

0;05% in total weight of the prepared mixture.

The Titanium dioxide for making the layer means, and/or the further layer means, and/or the still further layer means, is normally used in the form of a water colloidal solution, containing Titanium dioxide possibly in an amorphous state, in the form of Anatase, and/or a modified peroxytitanic acid and/or Titanium solution in the form of Rutile and/or of

Brookite.

Mixtures can be used that have a Titanium titre comprised between approximately 0.005% and approximately 12% by weight .

The Titanium found in the mixtures used to obtain the layer means, and/or the further layer means, and/or the still further layer means may all be in the form of 100% Anatase, or mixtures may be prepared containing Titanium in the form of Anatase and/or of Anatase peroxide in a percentage comprised between approximately 70% and approximately 90% and Titanium in the form of Rutile and/or peroxytitanic acid and/or Brookite in a percentage comprised between approximately 30% and approximately 10%.

Titanium dioxide can also be used in a possibly amorphous colloidal solution possibly containing additives, as specified above.

The compositions specified above can be used in association or separately.

The Titanium dioxide is used in the form of a water colloidal solution also in an amorphous state containing

Anatase and/or modified Anatase peroxide solution and/or peroxytitanic acid, and/or Rutile and/or Brookite.

The following solutions can, for example, be used that are known and are marketed by the company Jokero Invention

S.r.l. :

Titanium R: mainly used as a primer, i.e. for obtaining the still further layer means, a water solution in amorphous state containing a percentage by weight of TiO₂ comprised between approximately 0.5% to 9.70%, in particular containing approximately 0.85% by weight of TiO₂ as peroxytitanic acid, and H₂O for the remaining part;

Titanium R2 : mainly used as a primer, i.e. for obtaining the still further layer means, a water solution containing a percentage by weight of silicon gel, SiO₂, comprised between approximately 0.05% and approximately 19.90%, cationic surfactants in a percentage by weight comprised between approximately 0.05% and approximately 5.00%, acrylic resin in a percentage by weight comprised between approximately 0.05% and approximately 9.00%, sodium hydroxide NaOH in a percentage by weight comprised between approximately 0.005% and approximately 5.00%, and H₂O for the remaining part. In particular, the solution may contain the various compounds approximately in the following weighted percentages 7.50% SiO₂, 1.00% cationic surfactants, 0.10% NaOH, acrylic resin 1.50%, 89.90% H₂O.

Titanium K: a crystalline water solution containing a percentage by weight of TiO₂ comprised between approximately 0.5% and approximately 9.90%, in particular approximately 0.85% by weight of TiO₂ as modified Anatase peroxide, and H₂O for the remaining part;

Titanium KR: a mixed Titanium K and Titanium R water solution, containing a percentage by weight of TiO₂ comprised between approximately 0.05% and approximately 9.90%, in particular a percentage of approximately 0.85% by weight of a mixture consisting of approximately 70% modified Anatase peroxide solution and approximately 30% peroxytitanic acid, and H₂O for the remaining part;

Titanium KR-VB: a water solution containing a percentage by weight of TiO₂ comprised between approximately 0.05% and approximately 9.90%, in particular a percentage of approximately 0.85% by weight of a mixture consisting of approximately 70% modified Anatase peroxide solution and approximately 30% peroxytitanic acid and silver acetate C₂H₃AgO₂ in a percentage comprised between approximately 0.1% B2007/000935

10

and approximately 0.009% by weight and H₂O for the remaining part;

Titanium β: a water solution containing a percentage by weight of TiO₂ comprised between approximately 0.05% to approximately 9.5%, in particular a percentage di approximately 3.0% by weight of Titanium Degussa P25 (consisting of 80% Anatase and 20% Titanium oxide), and H₂O for the remaining part;

Titanium Ψ: a water solution containing a percentage by weight of TiO₂ comprised between approximately 0.01% and approximately 9.5%, in particular a percentage of approximately 0.5% by weight of Titanium in the form of Brookite, a percentage by weight comprised between approximately 0.001% and approximately 5.0% surfactant, for example [Ci₄H₂₂O(C₂H₄O)_n]A and a percentage by weight comprised between approximately 0.009% and approximately 0.1% of silver acetate C₂H₃AgO₂, H₂O for the remaining part;

Titanium Ω: a water solution containing approximately 1.49% by weight of TiO₂ in the form of Anatase, approximately 0.91% by weight of colloidal silicon SiO₂, approximately 0.05% by weight sodium hydroxide NaOH, approximately 0.13% by weight of lithium oxide Li₂O, approximately 0.015% by weight of sodium sulphite Na₂SO₃*7H₂O, approximately 0.03% by weight of sodium thiosulphate Na₂S₂O₃* 5H₂O, approximately 0.005% by weight of silver acetate C₂H₃AgO₂, water H₂O for the remaining part, approximately 97.37% by weight;

Titanium Ω₂: a water solution containing the following weighted percentages: Titanium dioxide such like Anatase of 1.06% ± 0.05%, colloidal silicon SiO₂ 1,93% ± 0.08%, sodium hydroxide NaOH 0.05%, lithium oxide Li₂O 0.22% + 0.02%, sodium sulphite Na₂SO₃*7H₂O 0.17% ± 0.01%, sodium thiosulphate Na₂S₂O₃* 5H₂O 0.42% ± 0.02%, silver acetate C₂H₃AgO₂ 0.037% ± 0.003%, sodium sulphate NaSO₄ 0.27% ± 0.002%, water H₂O for the remaining part approximately 97.37%. The semifinished products according to the invention enable the decomposition reactions of the substances to be accelerated, in particular of the organic polluting substances, which are completely oxidized until forming carbon dioxide (CO₂) and water (H₂O) , and of the inorganic polluting substances, and further enable any moulds, microbes, bacteria, and fungi to be eliminated, and gaseous and/or solid and/or liquid polluting substances coming into contact with the surface of the semifinished products to be decomposed.

The invention can be better understood and implemented with reference to the attached drawings, which show some embodiments thereof by way of non-limiting example, in which:

Figure 1 is a schematic side view of an embodiment of an apparatus for making footwear means;

Figure 2 is a frontal view of supplying means of the apparatus in Figure 1;

Figure 3 is a frontal view of heating means of the apparatus in Figure 1;

Figure 4 is a further frontal view of the supplying means of the apparatus in Figure 1 showing feeding means for feeding a photocatalytic solution to the supplying means;

Figure 5 is a frontal view of a further embodiment of the supplying means of the apparatus in Figure 1;

Figure 6 is a schematic view of another embodiment of an apparatus for making footwear means;

Figure 7 shows a control plate of the bacterial growth of colonies of Escherichia CoIi in agar;

Figure 8 shows a control plate of the bacterial growth of colonies of Escherichia CoIi in agar in the presence of UVA rays;

Figure 9 shows a plate for monitoring bacterial growth coated with Titanium dioxide TiO₂, after the plate has been placed in contact with Escherichia CoIi diluted 10% in suspension; Figure 10 shows a plate for monitoring bacterial growth coated with Titanium dioxide TiO₂, after a film containing Escherichia CoIi has been deposited on the plate; Figure 11 shows a plate for monitoring bacterial growth coated with Titanium dioxide TiO₂, after said plate has been placed in contact with Escherichia CoIi diluted 10% in suspension and has been kept in dark conditions in stationary conditions.

Figure 12 is a fragmentary schematic section of a first embodiment of semifinished products according to the invention;

Figure 13 is a fragmentary schematic section of a second embodiment of semifinished products according to the invention;

Figure 14 is a fragmentary schematic section of a third embodiment of semifinished products according to the invention;

Figure 15 is a fragmentary schematic section of a fourth embodiment of semifinished products according to the invention.

With reference to Figures 1 to 5, there is shown an embodiment of an apparatus 1 for treating semifinished products 2 comprising materials for making footwear elements and/or footwear, such as for example semifinished products made of leather, plastics, wood, cork, hide, multilayered semifinished products, for example having a part in latex and a part in hide, cork and natural rubber, PE, EVA, soft PU coupled with synthetic fibres or hide or other materials, footwear elements, such as for example, soles, arch- supports, heels, removable arch supports, orthopaedic arch- supports, soles, or also ready-assembled footwear, such as for example moccasins, gym shoes, hiking boots, ski boots, dancing pumps, traditional footwear generally for men and women, sport-footwear, high boots, footwear for motorcyclists, military footwear, sandals, mules, safety footwear, clogs, clogs in antistatic rubber for domestic and/or nursing use, closed slippers, open slippers, non-slip slippers .

The semifinished products 2 are supplied to a conveyor belt 3 moved between a pair of moving rollers 4, that are rotatable in a rotation direction indicated by the arrow F2 in Figure 1, that conveys the semifinished products 2 in the direction indicated by the arrow F to the various zones of the apparatus 1 in which the semifinished products 2 will be subjected to the action of the various treatment means 5 provided in the apparatus 1.

The treatment means 5 of the apparatus 1 comprises a plurality of applying means 8 arranged for applying a solution of photocatalytic material on the semifinished products 2 and a plurality of heating means 9, positioned along the conveyor belt 3 in an alternating manner with respect to the applying means 8 and arranged for emitting a flow of heating fluid, preferably hot and/or cold air, for heating the solution of photocatalytic material present on the semifinished products 2 and for promoting the evaporation thereof.

The plurality of the applying means 8 comprises in the embodiment shown in Figure 1, first applying means 10, second applying means 11, third applying means 12 and fourth applying means 13, having the same shape as one another and of which in Figures 1 and 2 there are shown different details for ease of representation. The plurality of the applying means 8 is insulated from the external environment by an insulating chamber 18 at the top of which there is provided a flue 19 for a controlled evacuation of gases that are generated by dispensing the solution.

The first applying means 10 and similarly the second, the third and the fourth applying means 11, 12, 13 may comprise, as shown in Figures 2 and 4, a multiplicity of supplying elements, 10' 10" and, respectively 12', 12'' arranged in the direction of the width L of the apparatus 1, i.e. in the direction that is transverse to the conveying direction F, in such a way as to ensure that all the surface of the semifinished products 2 is reached in a suitable manner by the photocatalytic solution, the surface being covered sufficiently therewith to ensure the efficacy thereof. This expedient is particularly useful if semifinished products 2 are treated from which obtaining a plurality of footwear elements is provided, for example semifinished products made of a sheet, or when simultaneously treating a plurality of footwear elements arranged in the width L of the apparatus 1 is provided.

Each of the applying means 10, 11, 12, 13 of the plurality of applying means 8 may further comprise, in the embodiment of Figure 5, described with greater detail below, a single supplying element 10''' that is movable in the width L, i.e. in a direction that is transverse to the conveying direction F for applying the photocatalytic solution to the entire surface of the semifinished products 2.

Each applying element of the plurality of applying means 8 is provided with an application nozzle 30 having a diameter D that is adjustable on the basis of the distance H of the nozzle 30 from the semifinished products 2, and on the basis of the extent and composition features of the semifinished products 2. The diameter D is variable between approximately 0.2 mm and approximately 1.5 mm.

At each of the applying means 10, 11, 12, 13 of the plurality of applying means 8, there is provided feeding means 20 for feeding the photocatalytic solution. The feeding means 20 comprises tanks 20 ' in which the various components of the photocatalytic solution, that has to be applied to the semifinished products 2, are collected and which are placed in communication with the applying means 10, 11, 12, 13, through the respective valves 21 configured in such a way as to appropriately dose the quantity of each component of the photocatalytic solution to be supplied to each of the applying means 10, 11, 12, 13, in order to obtain a solution having the desired composition and concentration .

The applying means 10, 11, 12, 13 is fixed to a bar 22 slidable along a pair of supporting rods 23 fixed to a base portion 24 of the apparatus 1. The bar 22 can be locked at a desired height of the aforesaid rods 23 by means of locking elements 25, in such a way as to vary the application height H of the applying means 10, 11, 12, 13 to adapt the application height H to the dimensions and to the features of the particular semifinished products 2 to be treated. Further, the position on the bar 22 of the supplying elements 10', 10' ' of each one of the applying means 10, 11, 12, 13 can be decided and suitably varied according to the features of the semifinished products 2 to be treated and, in particular, in order to ensure even covering of the semifinished products 2 with the photocatalytic solution. At each one of the applying means 10, 11, 12, 13 there are further provided controlling elements 26 for controlling the position of the supplying elements 10' , 10' , and the presence and features of the jet dispensed by the latter. In particular, controlling elements 26 comprises optical sensors 27 provided with first optical sensors 28, preferably positioned on the bar 22 adjacent to each supplying element 10', 10'', and arranged for detecting the width of the jet of solution supplied by each supplying element 10', 10", and thus for obtaining the extent of the surface of the semifinished products 2 reached by the solution, and second optical sensors 29 preferably positioned on the rods 23, that are movable along the rods 23 and that are arranged for checking the actual application of the jet of photocatalytic solution by each one of the supplying elements 10' , 10' ' .

The number of optical sensors provided for each of the applying means 10, 11, 12, 13 can be chosen on the basis of the features and dimensions of the coating means and/or of the features of the layer 200 of photocatalytic material that it is desired to obtain, and/or on the basis of the number of supplying elements 10', 10", 12', 12" that are actually provided.

The possible excess photocatalytic solution that is supplied externally to the surface occupied by the semifinished products 2 on the conveyor belt 3, and/or which drips from the semifinished products 2, as shown in Figure 1, collects on a conveying surface 3' of the conveyor belt 3 and, and as the latter is suitably drilled, gathers in a collection tank 31 provided below the conveyor belt 3.

The collection tank 31 can be provided with a recirculating system for recirculating the collected photocatalytic solution for drawing the solution collected 32 in the collection tank 31 and for feeding the solution collected 32 again to the applying means 8 of the apparatus 1. The plurality of heating means 9 comprises, in the embodiment shown in Figure 1, first heating means 14, second heating means 15, third heating means 16, fourth heating means 17, which may have the same or a different shape from one another, in particular, fan elements can be used as heating means 9, as shown in Figure 1, or heat exchanging elements or heating ovens.

The first heating means 14, and similarly the second, the third and the fourth heating means 15, 16, 17 may comprise, as shown in Figure 1, a multiplicity of heating elements 14' 14" and, respectively 15', 15", 16', 16", and 17', 17", arranged in the direction of the width L of the apparatus 1, i.e. in the direction that is transverse to the conveying direction F and/or in the conveying direction F, in such a way as to ensure that the entire surface of the semifinished products 2 is reached in a suitable manner by the flow of the heating fluid and that all the excess solution present on the semifinished products 2 evaporates between two subsequent application steps.

The heating means 14, 15, 16, 17 is connected at a further bar 35 slidable on a further pair of supporting rods 36 fixed to the base portion 24 of the apparatus 1, and which can be locked at a desired height of the aforesaid rods 36 through further locking elements 37, in such a way as to vary the application height Hl of the heating means 14, 15, 16, 17 with respect to the surface of the semifinished products 2 to be treated, in order to adapt the application height Hl to the dimensions and the features of the particular semifinished products 2 to be treated. The further supporting bar 35 of the heating means 14, 15, 16, 17 can be connected through a still further bar 35' , provided with still further locking elements 37', to the supporting rods 23 of the applying means 10, 11, 12, 13. At each of the heating means 14, 15, 16, 17 there are provided further controlling elements 33 for controlling the position of the heating elements 14', 14'' and 15', 15'', 16', 16'', and 17', 17'' and the presence and the width of the flow of fluid supplied by the heating elements 14', 14'' and 15', 15", 16', 16", and 17', 17", and, therefore, the extent of the surface of the semifinished products 2 reached in an effective manner by the flow.

In particular, the further controlling elements 33 comprise further optical sensors 34, preferably positioned on the further bar 35 adjacent to each heating element 14', 14", 15', 15", 16', 16", and 17', 17" in order to detect the width of the flow of heating fluid, and still further optical sensors, which are not shown, which are preferably positioned on the rods 36, are movable along them, and are arranged for checking the actual application of the heating fluid by each of the heating elements 14', 14", 15', 15", 16', 16", 17', 17".

At each of the heating means 14, 15, 16, 17, there can further be provided flow directing means for directing and concentrating the flow of the heating means to the surface of the coating means, in order to increase the effectiveness of the heating means 14, 15, 16, 17. The heating means 9 may further comprise in an embodiment that is not shown a single heating element that is movable in the direction L that is transverse to the conveying direction F for heating the photocatalytic solution that is present on the entire surface of the semifinished products 2.

With reference to Figure 5, there is shown an alternative embodiment of the applying means 10, 11, 12, 13, in which for each of the applying means 10, 11, 12, 13, there is provided a single supplying element 10''' provided with a body 38 that is fixed in a slidable manner to the bar 22 and from which an appendage 39 leads away that is anchored to a further conveyor belt 40 that is movable between further moving rollers 40' driven by an electric motor 41, in both senses of the direction indicated by the movement arrow Fl. There are further provided positioning sensors 42 positioned on the bar 22 and arranged for determining the stroke start/end of the supplying element 10''', the position of the positioning sensors 42 and therefore the position of the stroke start/end of the supplying element 10''' can be selected and varied suitably on the basis of the dimensions of the semifinished products 2 to be treated.

Also in this embodiment there are provided the controlling elements 26 for controlling the operation of the supplying element 10'''. The controlling elements 26 comprise first optical sensors 28, possibly incorporated in or connected to the positioning sensors 42 connected to the bar 22 and arranged for determining the presence of the application jet, and second optical elements 29 fixed to the rods 23 and arranged for determining the width of the application jet. In operation, the semifinished products 2 are supplied to the conveyor belt 3 in such a way as to rest on the conveying surface 3' of the conveyor belt 3.

The conveyor belt 3 takes the semifinished products 2 in succession first to a first application zone in which there is provided the first supplying means 10 that applies the solution of photocatalytic material, successively to a first heating zone in which the first heating means 14 heats the solution on the surface of the semifinished products 2 to make the excess solvent evaporate therefrom.

This sequence of operations can be repeated for a desired number of times, depending on the dimensions and features of the semifinished products 2, and also on the features of the layers of solution that it is desired to generate to the semifinished products 2, as shown in Figures 12 to 15 explained below.

After the operations disclosed above, the semifinished products 2 are conveyed, still by the conveyor belt 3, to a further heating zone 45, in which further heating means 46, for example, an oven 47, further heat the semifinished products 2 that are now provided with the layer and/or the layers of photocatalytic material, to consolidate the structure thereof and to strengthen the adhesion of the photocatalytic material to the surface of the semifinished products 2.

As shown in Figure 12, the photocatalytic layer 200 can be applied, according to the methods seen above, to the semifinished product 2, and in particular to a surface 2a thereof suitable for coming, in use, into contact with a user.

Or, as shown in Figure 13, there can be provided an intermediate further layer 201 interposed between the semifinished products 2 and the photocatalytic layer 200, for preserving the material of the semifinished products 2 from possible chemical attacks and for promoting the adhesion of the layer 200 in photocatalytic material to the semifinished products 2.

Or, as shown in Figure 14, there can be provided an intermediate still further layer 202, acting as a primer, interposed between the semifinished products 2 and the photocatalytic layer 200. Or, as shown in Figure 15, there can be provided the intermediate further layer 201 and also the intermediate still further layer 202, arranged in such a way that the intermediate still further layer 202 is interposed between the semifinished products 2 and the intermediate further layer 201.

As can be seen, in each embodiment the photocatalytic layer 200 is arranged on the semifinished products 2 in such a way as to come into contact in use with a user, so as to perform its antifungal, antibacterial, odour-eating, etc. properties .

The intermediate still further layer 202 acts as a "primer", and preserves the material of the semifinished products 2 from possible chemical attacks and promotes the adhesion to the latter of the layer 200 made of photocatalytic material. The further layer 201 and/or the still further layer 202 being obtained by applying to the semifinished products 2, according to any suitable method, for example in the manner seen above, or through spraying, through immersion, a Titanium dioxide-based solution containing Titanium in the form of Rutile, and/or any one of the other solutions containing Titanium disclosed above.

After applying, drying the further layer 201, and/or the still further layer 202, is provided, using respective heating means in order to promote the evaporation of the excess solvent.

These operations precede applying the layer 200 of photocatalytic solution, therefore, the means intended for applying and drying the further layer and/or the still further layer are provided upstream of the applying means 8 and of the heating means 9.

In some embodiments some of the applying means 10, 11, 12, 13 can be used to apply the further layer 201 and/or the still further layer 202.

The applying means for applying the further layer 201 and/or of the still further layer 202 can have a shape similar to that seen for the applying means 10, 11, 12, 13 disclosed above.

Similar considerations can be further made for the heating means arranged for heating the solution of the further layer 201 and/or of the still further layer 202.

With reference to Figure 6, there is shown an alternative embodiment of an apparatus 100 for treating semifinished products 2, in which the same parts of the apparatus in Figure 1 are indicated by the same numeric references, and which differs from the embodiment in Figure 1 mainly through the fact that the layer 200 of photocatalytic material is made on the semifinished products 2 by immersing the semifinished products 2 in a tank 50 containing a definite quantity of photocatalytic material solution. The apparatus comprises a conveyor belt 3, moved between a plurality of moving rollers 4' arranged together in such a way as to keep tensioned the conveyor belt 3 and to make the semifinished products 2 to be conveyed along a sinuous path through the treatment means 5 provided in the apparatus 100. The moving rollers 4' are provided with cleaning means, comprising for example scrapers 61, arranged for scraping an external surface 63 of the moving rollers 4' in order to remove possible particles that have detached from the semifinished products 2 and that may ruin the surface 63 of the moving rollers 4, and the conveyor belt and adversely affect the conveying of the semifinished products 2. The material scraped by the scrapers 61 is collected in suitable containers 62 provided near the scrapers 61. The treatment means 5 comprises preheating means 48 that can be configured as a preheating oven 49, as shown in Figure 6, or as heat exchangers, or as fans, which preheat the semifinished products 2 in order to prepare the semifinished products 2 for the application of the solution of photocatalytic material in the tank 50 in which the semifinished products 2 are immersed to receive the photocatalytic solution. The tank 50 is filled up to the level indicated by Z with the solution of photocatalytic material and is supplied through suitable application valves 21 by the tanks 20' in which the components of this solution are collected, these valves 21 being so shaped as to maintain constant in the tank 50 the level Z and the concentration of the photocatalytic solution.

In order to convey the semifinished products 2 inside the tank 50, there is provided a plurality of belts 57 that divert the path of the semifinished products 2 until they are conveyed inside the tank 50 in which they are immersed inside the photocatalytic solution.

The semifinished products 2, that have been previously heated by the preheating device 49, are kept immersed in the chosen photocatalytic solution for a time varying from 1 second to 100 minutes in such a way that the semifinished products 2 absorb the necessary quantity of photocatalytic solution.

The semifinished products 2 are subsequently conveyed by the perforated belt 57 in the direction indicated by the evacuating arrow F3 towards drying devices 7, whilst the particles of material having dimensions that are less than those of the holes of the perforated belt 57 fall and gather at the bottom of the tank 50.

The tank 50 is further provided with a system for circulating the solution, comprising a pump 53 that removes the solution from the bottom of the tank 50 and pumps the solution so as to discharge it near the surface of the tank 50, and with a first filtering system 55 positioned upstream of the suction section of the pump 53, and with a second filtering system 56 positioned downstream of the delivery section of the pump 53, arranged for filtering the solution to eliminate possible foreign bodies, and the particles detached from the semifinished products 2 during the immersion in the tank 50. The tank 50 is further provided with an inspection hatch 54 for cleaning and routine and/or special maintenance operations of the tank 50.

The semifinished products 2, provided with the layer 200 of photocatalytic solution, are conveyed to heating devices 7 that comprise heating means 59 for making the excess photocatalytic solution evaporate, and further heating means 60 for completing the aforesaid operation and for increasing adhesion of the layer 200 of photocatalytic material to the semifinished products 2 and the solidification of this layer.

As can be seen, in this embodiment the photocatalytic solution is applied to the semifinished products 2 through immersion and can occur in a single operation. Also in this case, on the semifinished products 2 the further layer 201 and/or the still further layer 202 can be provided to enhance the adhesion of the layer 200 of photocatalytic material to the semifinished products 2, and to preserve the material of the semifinished products 2 from possible damage, these operations being provided upstream of those previously disclosed.

The further layer 201 and/or the still further layer 202 can be applied by using applying means having a configuration similar to that of the applying means 10, 11, 12, 13, previously disclosed, and/or using applying means comprising further tanks in which is collected the solution to be applied, and in which the semifinished products 2 are subsequently immersed.

The selected combination of operations and the type of operations run and the repetition thereof are decided on the basis of the features of the single semifinished products and the features of the semifinished products that it is wished to obtain at the end of treatment.

It should be noted that in both presented embodiments of an apparatus for treating the semifinished products 2, if the application of the further layer 201 and/or of the still further layer 202 is provided, the heating operation of the further layer 201 and/or of the still further layer 202 for making the excess solvent thereof evaporate may constitute the operation of preheating the semifinished products 2 prior to the first application of the photocatalytic solution of Figure 1, or to the application of the photocatalytic solution by immersion, Figure 6.

The layer 200 of photocatalytic material, and/or the further layer 201, and/or the still further layer 202 are made with one or more Titanium dioxide based liquid solutions like those quoted above.

The concentration of the Titanium-based compounds in the photocatalytic solution may vary on the basis of the application conditions and on the basis of the composition and the material of the semifinished products 2, of the particular desired future use of the semifinished products

2, and on the basis of other process features.

The thickness of the layer of photocatalytic material may preferably vary from approximately 0.02μ to approximately

3.0μ thick.

With reference to Figures 7 to 11 there are shown plates 100 in agar that have been used to evaluate the bacterial growth of Escherica CoIi in five different experimental conditions.

Firstly a culture of microorganisms has been obtained by sowing the microorganisms in approximately 6-8 ml of a culture broth contained in a test tube, that has been placed in an environment thermo-stabilized at 37⁰C, i.e. at the optimal environmental conditions for bacterial growth, and stirred for 6 to 8 hours.

At the end, the solution in the test tube is visibly turbid due to the presence of a large quantity of bacteria.

A constant fixed quantity of the bacteria-rich solution was then sown in various glass Petri plates to determine the further bacterial growth in various environmental conditions . In a first experiment, the results of which are shown in Figure 7, the bacteria-rich solution was sown in a plate containing only the culture medium; the plate was then positioned in a thermo-stabilized oven at 37⁰C for 14 hours in a stirred state, or stationary state, and kept in dark conditions .

After this interval of time had elapsed, from the plate constant quantities of solution were taken that were then diluted and sowed in an agar bed, a plate, for determining the number of living bacteria present, and the sown plate was then placed in a thermo-stabilized chamber at 37⁰C for 24 hours.

After this period of time had elapsed, the plate appeared as shown in Figure 7, i.e. rich in bacterial colonies that had developed during the duration of the experiment. In a second experiment, the results of which are shown in Figure 8, the bacteria-rich solution was sown in a plate containing only the culture medium; the plate was then positioned in a thermo-stabilized oven at 37⁰C for 14 hours, in a stirred, or stationary state, and irradiated with sources of UVA rays filtered by the infrared component with water filters to prevent local overheating.

After this interval of time had elapsed, from the plate constant quantities of solution were taken that were then diluted and sown in an agar medium, a plate, for determining the number of live bacteria present, and the sown plate was then placed in a thermo-stabilized chamber at 37⁰C for 24 hours .

After this period of time had elapsed the plate appeared as shown in Figure 8, i.e. rich in bacteria colonies that had developed during the duration of the experiment. In a third experiment, the results of which are shown in Figure 9, the bacteria-rich solution was sown on a plate that had been previously treated with a Titanium dioxide and silver solution, in particular with a solution containing 1 ml of the two different products, and then heated and dried up to 6O⁰C. The plate was then positioned in a thermo- stabilized oven at 37 °C for 14 hours in a stirred, or stationary state, and irradiated with sources of UVA rays filtered by the infrared component with water filters to prevent local overheating.

After this period of time had elapsed the plate appeared as shown in Figure 9, i.e. free of bacterial colonies, which had been eliminated by the presence of the Titanium and silver based compounds.

Similar results, i.e. complete elimination of the bacteria colonies due to the presence of the Titanium and silver based compounds, are also obtained if the solution of Echerica CoIi is placed as a film on the agar plate, as shown in Figure 10.

Similar results, i.e. complete elimination of the bacteria colonies due to the presence of the Titanium and silver based compounds, are also obtained if the agar plate is kept in dark conditions, as shown in Figure 10.

This result is particularly important because it demonstrates that the efficacy of the Titanium-based and possibly silver-based compounds in eliminating bacteria is not necessarily linked to the presence of luminous radiation.

For the experiments commented on above, the layer of photocatalytic material is made with a Titanium dioxide- based liquid solution in the form of Anatase, and/or colloidal solutions of modified Anatase peroxide and/or of peroxytitanic acid in water, these solutions being possibly mixed with silver compounds. The experiments were repeated using Titanium and/or silver products, both in liquid and in solid form, and with different concentration values. The actual concentration of the Titanium based compounds for preparing the photocatalytic solution may vary according to application conditions, the composition and the features of the semifinished products, the footwear elements and/or the footwear, the particular hypothetical future use of the semifinished products, of the footwear elements and/or of the footwear, and on the basis of other process features. The concentration of the Titanium based compounds in the photocatalytic solution varies from approximately 0.05% by weight to approximately 9.90% by weight.

Thus the semifinished products, the footwear elements and/or the footwear obtained according to the invention can perform the bactericide, fungicide function without having to be subjected to particular treatments between successive uses. Thus a user of the semifinished products, of the footwear elements, of the footwear according to the invention who after use places, for example, the footwear in shoe racks or cabinets also in even dark conditions, when he takes the footwear out for subsequent use will find the footwear free of bacteria or fungi and, above all, will find that the footwear does not exhale bad odours .

The Titanium dioxide is a semiconductor material with a crystalline structure, having a valence band that is separated by a conducting band from a set energy difference. Like most materials, when Titanium dioxide is hit by electromagnetic radiation it absorbs energy from the radiation. When the absorbed energy is greater than the energy difference between the valence band and the conducting band, an electron is promoted from the valence band to the conducting band, generating an excess electronic load (e^~) in the conducting band and an electron gap (h⁺) in the valence band. The Titanium dioxide is solid state at ambient temperature in crystalline form as Anatase, Rutile or Brookite. Anatase is the crystalline form that is most active from the photocatalytic point of view and has an energy difference between the valence band and the conducting band of 3.2 eV. As a result, if the Anatase is irradiated with photons having energy greater than 3.2 eV, i.e. with electromagnetic radiation with a wavelength of less than 390 nrα, an electron is promoted from the valence band to the conducting band. This occurs in particular when the Titanium dioxide is hit by ultraviolet radiation (UV) , for example emitted by an ultraviolet ray lamp, or by solar radiation. The electronic gaps can oxidize most organic contaminants. These electronic gaps may, for example, react with a water molecule (H₂O), generating a hydroxyl radical ('0H) that is highly reactive. The excess electrons have a very great reducing power and can react with the molecule of the oxygen to form the superoxide anion (O₂'^") ι. The oxidation reaction of the water molecule is shown in the formula (I) and the reaction of the oxygen is shown in the formula (II) :

TiO₂ (h⁺) + H₂O ^■* TiO₂ + ^«0H + H⁺; (I)

TiO₂ (e^~) + O₂ ^•* Ti02 + O₂ ^" (II)

The hydroxyl radical (^#0H) is particularly active both for oxidising organic and inorganic substances, for example present in air, and for deactivating microorganisms that may, for example, be poisonous for cultivated plants and for humans .

In particular, organic compounds are oxidized to carbon dioxide (CO₂) and water (H₂O), nitrogen compounds are oxidized to nitrate ions (NO₃ ^") , sulphur compounds to sulphate ions (SO₄ ^2") . Titanium dioxide is further able to decompose many gases or harmful substances, such as thiols or mercaptans, formaldehyde, having an unpleasant smell. The decomposition of these gases or substances eliminates the bad smells associated therewith.

The Titanium also performs an antimicrobe, antibacteria and anti-mould function that is very effective as unlike other antibacterial agents it does not kill the bacteria or mould but through oxidoreduction, Titanium decomposes them into gaseous substances that are dispersed into the surrounding environment, not collecting in the catalyst.

This further enables the photocatalytic activity of the

Titanium to be maintained unaltered over time .

In particular, the decomposition of the bacteria occurs by means of hydroxide radicals (OH*) and oxygen anions (O₂ ^") generated by the photocatalytic process that attack the lipid membrane of the bacteria, decomposing it and preventing the aerobic breathing phase of the bacteria.

The microorganisms thus die and are then gradually decomposed until carbon dioxide and water are obtained that are liberated into the surrounding environment.

The destruction of the moulds, the bacteria, the viruses and the other microorganisms enables the bad smells to be eliminated that are associated therewith, and to maintain a high hygienic level in the substrate to which the Titanium dioxide has been applied.

Further to that, the Titanium has pronounced hydrophilicity, i.e. a total lack of water repellence, this feature occurs above all after exposure to radiation and provides the semifinished products, the footwear elements, and/or the footwear with a layer in self-cleaning Titanium.

The behaviour of a material with respect to wetting is determined by the surface tensions existing at the interfaces between the material and the water and the surrounding environment, for example air, the ratio between two surface tension values indicated above determines the contact angle (θ) .

When the contact angle is zero, wetting is complete and the water spreads as a coating over the surface of the material, whereas as the contact angle decreases, wetting decreases and the water contracts into drops that remain on the surface of the material.

Titanium, in the crystalline form of Anatase has, if exposed to radiation, contact angles with respect to the water that are very small, less than 1°, i.e. the Titanium attracts the water rather than repelling it; this feature, which is known as superhydrophilicity, enables, for example antifogging mirrors to be made, and in particular, if the Titanium is applied to coating means enables the trapped pollutants trapped within the water molecules and/or the products of photocatalytic degradation to be easily cleaned off the coating means simply by washing off.

The feature of the superhydrophilicity of the Titanium in the form of Anatase is based on excitation of electrons from the valence band to the conducting band following irradiation with consequent creation of gaps of electrons (h⁺) and of electrons (e^~) that react in the manner explained below, leading to the expulsion of the Titanium dioxide Anatase molecule of an oxygen atom and the creation of an "oxygen vacancy". e^" + Ti^{4+ ■}* Ti³⁺; 4h⁺ + 2O₂ ^{2" ■}-► O₂T

The oxygen vacancies are replaced by dissociated water molecules (OH^") that make the surface hydrophilous. This feature increases with exposure to radiation, because as exposure continues, the contact angle decreases, which after approximately 30 minutes of exposure, tends to zero, i.e. the water tends to form a continuous coating on the surface of the material, covering the surface thereof almost completely. ,

Claims

1. Semifinished products, comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprising a support made of a desired material and characterised in that comprise layer means (200, 201, 202) having photocatalytic functions arranged on said semifinished products.

2. Semifinished products according to claim 1, wherein said layer means (200, 201, 202) comprises Titanium dioxide compounds .

3. Semifinished products according to claim 1, or 2, wherein said layer means (200, 201, 202) comprises Titanium dioxide compounds in the form of Anatase.

4. Semifinished products according to any one of claims 1 to 3, wherein said layer means (200, 201, 202) comprises Titanium dioxide compounds in the form of modified peroxytitanic acid.

5. Semifinished products according to any one of claims 1 to 4, wherein said layer means (200, 201, 202) is provided on a surface (2a) of said semifinished products (2) suitable for coming into contact in use with a user of said semifinished products.

6. Semifinished products according to any one of claims 1 to 5, and further comprising further layer means (201) interposed between a surface of said semifinished products (2a) and said layer means (200) .

7. Semifinished products according to claim 6, wherein said further layer means (201) comprises Titanium dioxide.

8. Semifinished products according to claim 6, or 7, wherein said further layer means (201) comprises compounds having great adhesive power and which are not oxidizable.

9. Semifinished products according to any one of claims 6 to 8, wherein said further layer means (201) comprises Titanium dioxide in the form of Rutile.

10. Semifinished products according to any one of claims 1 to 9, and further comprising still further layer means (202) interposed between a surface (2a) of said semifinished products (2) and said layer means (200) .

11. Semifinished products according to any one of claims 1 to 9, and further comprising still further layer means (202) interposed between a surface (2a) of said semifinished products (2) and said further layer means (201) .

12. Semifinished products according to claim 10, or 11, wherein said further layer means (202) comprises compounds having great adhesive power and which are not oxidizable.

13. Semifinished products according to any one of claims 10 to 12, wherein said still further layer means (202) comprises Titanium dioxide compounds.

14. Semifinished products according to any one of claims 10 to 13, wherein said still further layer means (202) comprises Titanium as peroxytitanic acid.

15. Semifinished products according to any one of claims 10 to 14, wherein said still further layer means (202) comprises a silicon-based compound.

16. Semifinished products according to any one of claims 10 to 15, wherein said still further layer means (202) comprises a primer.

17. Semifinished products according to any one of claims 1 to 16, wherein said layer means (200, 201, 202) comprises Titanium dioxide in the form of Brookite.

18. Semifinished products according to any one of claims 1 to 17, wherein said layer means (200, 201, 202) comprises surfactants.

19. Semifinished products according to any one of claims 1 to 18, wherein said layer means (200, 201, 202) comprises additives.

20. Semifinished products according to claim 19, wherein said additives comprise a solution in suitable solvents, and/or powder compounds, and/or compounds in the shape of microspheres, and/or laminas, a solution in suitable solvents.

21. Semifinished products according to claim 19, or 20, wherein said additives comprise gripping materials.

22. Semifinished products according to any one of claims 19 to 21, and further comprising silicon and/or colloidal silicon.

23. Semifinished products according to any one of claims 19 to 22, wherein said additives comprise silver-based compounds (Ag) and/or a derivative thereof.

24. Semifinished products according to any one of claims 19 to 23, wherein said additives comprise at least a silver salt, such as, for example, silver acetate (CH₃COOAg) .

25. Semifinished products according to claim 23, wherein said silver-based compounds have a concentration comprised between approximately 0.001% and approximately 0.5% by weight.

26. Semifinished products according to claim 24, wherein said silver acetate is present in a percentage comprised between approximately 0.005% and approximately 0.1% by weight.

27. Semifinished products according to any one of claims 19 to 26, wherein said additives comprise copper (Cu) , and/or a derivative thereof, and/or copper-based compounds .

28. Semifinished products according to any one of claims 19 to 26, wherein said additives comprise, copper oxide (CuO), or a copper salt (II), for example CuSO₄.

29. Semifinished products according to claim 27, or 28, wherein said additives are present in a concentration comprised between approximately 0.001% and approximately 0.5% in total weight of the prepared mixture .

30. Semifinished products according to claim 27, or 28, wherein said additives are present in a concentration comprised between approximately 0.005% and approximately 0.1% by weight.

31. Semifinished products according to any one of claims 1 to 30, wherein said layer means (200, 201, 202) comprises antibacterial, anti-mould, odour-eating, antifungal substances .

32. Semifinished products according to any one of claims 1 to 31, wherein said layer means (200, 201, 202) comprises substances with a surfactant action.

33. Semifinished products according to claim 32, wherein said substances with a surfactant action are present in a concentration comprised between approximately 0.001% and approximately 5% by weight.

34. Semifinished products according to any one of claims 1 to 33, wherein said layer means (200, 201, 202) comprises silicon (SiC>2) .

35. Semifinished products according to any one of claims 1 to 33, wherein said layer means (200, 201, 202) comprises silicon (SiO₂) in colloidal form.

36. Semifinished products according to claim 34, or 35, wherein said layer means (200, 201, 202) comprises silicon (SiO₂) in a concentration comprised between approximately 0.5% and approximately 2.0% by weight.

37. Semifinished products according to any one of claims 1 to 36, wherein said layer means (200, 201, 202) further comprises a component chosen from a group comprising sodium hydroxide (NaOH) , lithium oxide (Li₂O) , sodium sulphite heptahydrate (Na₂S₂O₃^H₂O), sodium thiosulphate pentahydrate (Na₂SO₃* 5H₂O) .

38. Semifinished products according to any one of claims 1 to 36, wherein said layer means (200, 201, 202) comprises sodium hydroxide (NaOH) in a concentration comprised between approximately 0.01% and approximately 0.1% by weight.

39. Semifinished products according to any one of claims 1 to 36, wherein said layer means (200, 201, 202) comprises lithium oxide (Li₂θ) in a concentration comprised between approximately 0.01% and approximately 1.0% by weight.

40. Semifinished products according to any one of claims 1 to 36, wherein said layer means (200, 201, 202) comprises sodium sulphite heptahydrate (Na₂S₂O₃* 7H₂O) in a concentration comprised between 0.01% and approximately 0.1% by weight.

41. Semifinished products according to any one of claims 1 to 36, wherein said layer means (200, 201, 202) comprises sodium thiosulphate pentahydrate (Na₂Sθ₃ ^#5H₂θ) in a concentration comprised between 0.001% and 0.05% by weight.

42. Semifinished products according to any one of claims 1 to 41, wherein said layer means (200, 201, 202) is Titanium dioxide in a colloidal water solution.

43. Semifinished products according to any one of claims 1 to 42, wherein said layer means (200, 201, 202) is amorphous Titanium dioxide in a colloidal water solution.

44. Semifinished products according to any one of claims 1 to 43, wherein said layer means (200, 201, 202) comprises Titanium dioxide as a modified peroxytitanic acid solution.

45. Semifinished products according to any one of claims 1 to 44, wherein said layer means (200, 201, 202) comprises Titanium dioxide in the form of Anatase and/or Anatase peroxide.

46. Semifinished products according to any one of claims 1 to 45, wherein said layer means (200, 201, 202) comprises Titanium dioxide in the form of Brookite.

47. Semifinished products according to any one of claims 1 to 46, wherein said layer means (200, 201, 202) comprises Titanium dioxide in the form of Rutile.

48. Semifinished products according to any one of claims 1 to 47, wherein said layer means (200, 201, 202) comprises Titanium dioxide as Anatase o Anatase peroxide in a percentage comprised between approximately 60% and approximately 95%, and/or Titanium dioxide as Rutile and/or as peroxytitanic acid and/or as Brookite in a percentage comprised between approximately 40% and approximately 5%.

49. Semifinished products according to any one of claims 1 to 47, wherein said layer means (200, 201, 202) comprises Titanium dioxide as Anatase o Anatase peroxide in a percentage comprised between approximately 70% and approximately 90%, and/or Titanium dioxide as Rutile and/or as peroxytitanic acid and/or as Brookite in a percentage comprised between approximately 30% and approximately 10%.

50. Semifinished products according to any one of claims 1 to 49, wherein said layer means (200, 201, 202) comprises Titanium dioxide in a percentage comprised between approximately 0.005% and approximately 12% by weight .

51. Semifinished products according to any one of claims 1 to 50, wherein said layer means (200, 201, 202) is obtained from a water solution in amorphous state comprising Titanium dioxide as peroxytitanic acid comprised between approximately 0.5% to 9.70% by weight, and H₂O for the remaining part.

52. Semifinished products according to any one of claims 1 to 50, wherein said layer means (200, 201, 202) is obtained from a water solution in amorphous state comprising Titanium dioxide as peroxytitanic acid at approximately 0.85% by weight, and H₂O for the remaining part.

53. Semifinished products according to any one of claims 1 to 52, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage by weight of silica gel comprised between approximately 0.05% and approximately 19.90%, cationic surfactants in a percentage by weight comprised between approximately 0.05% and approximately 5.00%, acrylic resin in a percentage by weight comprised between approximately 0.05% and approximately 9.00%, sodium hydroxide NaOH in a percentage by weight comprised between approximately 0.005% and approximately 5.00%, and H₂O for the remaining part.

54. Semifinished products according to any one of claims 1 to 52, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage by weight of silica gel of approximately 7.50%, cationic surfactants at approximately 1.00%, NaOH at approximately 0.10%, acrylic resin at approximately 1.50%, and H₂O at 89.90%.

55. Semifinished products according to any one of claims 1 to 54, wherein said layer means (200, 201, 202) is obtained from a crystalline water solution containing a percentage of Titanium dioxide as modified Anatase peroxide comprised between approximately 0.5% and approximately 9.90% by weight, and H₂O for the remaining part.

56. Semifinished products according to any one of claims 1 to 54, wherein said layer means (200, 201, 202) is obtained from a crystalline water solution containing a percentage of Titanium dioxide as modified Anatase peroxide of approximately 0.85% by weight, and H₂O for the remaining part .

57. Semifinished products according to any one of claims 1 to 56, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide by weight of a mixture consisting of approximately 70% from a solution of modified Anatase peroxide and of approximately 30% peroxytitanic acid.

58. Semifinished products according to claim 57, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide comprised between approximately 0.05% and approximately 9.90% by weight, and H₂O for the remaining part.

59. Semifinished products according to claim 57, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide of approximately 0.85% by weight, and H₂O for the remaining part .

60. Semifinished products according to any one of claims 1 to 59, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage by weight of Titanium dioxide of a mixture consisting of approximately 70% from a solution of modified Anatase peroxide and approximately 30% Peroxytitanic acid, and silver acetate C₂H₃AgO₂.

61. Semifinished products according to claim 60, wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide comprised between approximately 0.05% and approximately 9.90% by weight, and H₂O for the remaining part.

62. Semifinished products according to claim 60 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide of approximately 0.85% by weight, and H₂O for the remaining part.

63. Semifinished products according to any one of claims 1 to 62 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide approximately at 80% as Anatase and approximately at 20% as Rutile, comprised between approximately 0.05% and approximately 9.5% by weight, and H₂O for the remaining part.

64. Semifinished products according to claim 63 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide of approximately 3.0% by weight, and H₂O for the remaining part.

65. Semifinished products according to any one of claims 1 to 64 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide approximately 80% as Anatase and approximately 20% as Rutile, comprised between approximately 0.05% and approximately 9.5% and H₂O for the remaining part.

66. Semifinished products according to any one of claims 1 to 65 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide in the form of Brookite comprised between approximately 0.01% and approximately 9.5% by weight, a percentage comprised between approximately 0.001% and approximately 5.0% by weight of surfactant, for example [Ci₄H₂₂O (C₂H₄O)_n] , a percentage comprised between approximately 0.009% and approximately 0.1% by weight of silver acetate C₂H₃AgO₂, and H₂O for the remaining part .

67. Semifinished products according to any one of claims 1 to 65 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide in the form of Brookite of approximately 0.5% by weight, a percentage comprised between approximately 0.001% and approximately 5.0% by weight of surfactant, for example [Ci₄H₂₂O(C₂H₄O)_n], a percentage comprised between approximately 0.009% and approximately 0.1% by weight of silver acetate C₂H₃AgO₂, and H₂O for the remaining part.

68. Semifinished products according to any one of claims 1 to 67 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage of Titanium dioxide as Anatase of approximately 1.49% by weight, approximately 0.91% by weight of colloidal silica SiO₂, approximately 0.05% by weight of sodium hydroxide NaOH, approximately 0.13% by weight of lithium oxide Li₂O, approximately 0.015% by weight of sodium sulphite Na₂SO₃* 7H₂O, approximately 0.03% by weight of sodium thiosulphate Na₂S₂O₃ '5H₂O, approximately 0.005% by weight of silver acetate C₂H₃AgO₂, water H₂O for the remaining part.

69. Semifinished products according to any one of claims 1 to 68 wherein said layer means (200, 201, 202) is obtained from a water solution containing a percentage by weight of Titanium dioxide in the form of Anatase comprised between approximately 1% and approximately 1.15%, colloidal silica comprised between approximately 1.85% and approximately 2.05%, sodium hydroxide NaOH approximately 0.05%, lithium oxide Li₂O comprised between approximately 0.20% and approximately 0.25%, sodium sulphite Na₂SO₃* 7H₂O between approximately 0.15% and approximately 0.20%, sodium thiosulphate Na₂S₂O₃* 5H₂O between approximately 0.40% and approximately 0.45%, silver acetate C₂H₃AgO₂ between approximately 0.032% and approximately 0.040%, sodium sulphate NaSO₄ between approximately 0.25% and approximately 0.30%, water H₂O for the remaining part, approximately 97.37%.

70. Footwear means comprising footwear elements, characterised in that it comprises layer means (200, 201, 202) having photocatalytic functions arranged on said footwear elements.

71. Footwear means according to claim 71, and further comprising semifinished products (2) according to any one of claims 1 to 69.

72. Footwear means according to claim 70, and further comprising layer means (200, 201, 202) according to any one of claims 1 to 69.

73. Apparatus for treating semifinished products (2) comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprising moving means (3, 4; 3, 4') for moving along a desired path (F) said semifinished products (2) and characterised in that it comprises applying means (8, 10, 11, 12, 13; 8, 50) arranged along said path (F) for applying a solution (200, 201, 202) of a photocatalytic material to said semifinished products (2) .

74. Apparatus according to claim 73, and further comprising heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) arranged along said path (F) and suitable for heating said solution to make the excess solvent thereof evaporate.

75. Apparatus according to claim 73, or 74, wherein said applying means comprises a plurality of applying means (10, 11, 12, 13) arranged for applying a solution of a photocatalytic material to said semifinished products (2).

76. Apparatus according to claim 75, wherein said applying means (8) of said plurality of applying means (10, 11,

12, 13) comprises a multiplicity of feeding elements

(10', 10", 12', 12") that are movable in at least one desired direction for applying a solution of a photocatalytic material to said semifinished products (2) .

77. Apparatus according to claim 75, wherein said applying means of said plurality of applying means (10, 11, 12, 13) comprises a feeding element (10''') that is movable in at least a desired direction for applying a solution of a photocatalytic material to said semifinished products (2) .

78. Apparatus according to any one of claims 73 to 77, wherein said applying means comprises containing means

(50) arranged for containing a solution of photocatalytic material.

79. Apparatus according to claim 78, and further comprising immersion means (57) arranged for immersing said semifinished products (2) in said containing means (50) .

80. Apparatus according to claim 78, or 79, wherein said heating means comprises heating devices (48, 49) provided upstream of said containing means (50) for heating said semifinished products (2) .

81. Apparatus according to any one of claims 78 to 80, wherein said heating means comprises further heating devices (60) provided downstream of said containing means (50) for heating said semifinished products (2).

82. Apparatus according to any one of claims 74 to 81, wherein said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) comprises fans, heating ovens, heat exchangers .

83. Apparatus according to any one of claims 74 to 82, and further comprising controlling means (33, 34, 42) arranged for controlling the position of said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) .

84. Apparatus according to claim 83, wherein said controlling means (33, 34, 42) comprises optical sensors .

85. Apparatus according to claim 83, or 84, wherein said controlling means comprises first controlling means for controlling the position of said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) in a desired direction.

86. Apparatus according to claim 85, wherein said controlling means comprises second controlling means for controlling the position of said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) in a further desired direction.

87. Apparatus according to any one of claims 74 to 86, and further comprising inspection means arranged for inspecting the operation of said heating means (9, 14,

15, 16, 17; 7, 45, 46, 47, 49, 60).

88. Apparatus according to claim 87, wherein said inspection means comprises optical sensors.

89. Apparatus according to any one of claims 74 to 88, and further comprising moving means arranged for moving said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) in a desired direction.

90. Apparatus according to claim 89, and further comprising further moving means arranged for moving said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) in a further desired direction that is different from said desired direction.

91. Apparatus according to any one of claims 74 to 90, and further comprising locking means (37' ) arranged for locking said heating means (9, 14, 15, 16, 17; 7, 45, 46, 47, 49, 60) in a desired heating position.

92. Apparatus according to any one of claims 74 to 91, wherein said heating means (9) comprises a plurality of heating means (14, 15, 16, 17) arranged for heating a solution of a photocatalytic material on said semifinished products (2) .

93. Apparatus according to claim 92, wherein said heating means (9) of said plurality of heating means (14, 15,

16, 17) comprises a multiplicity of heating elements (14', 14", 15', 15", 16', 16", 17', 17") arranged for heating a solution of a photocatalytic material on said semifinished products (2) .

94. Apparatus according to claim 92, or 93, as claim 92 is appended to any one of claims 79 a 82, wherein said applying means of said plurality of applying means (10, 11, 12, 13) is arranged on said path (F) in a alternating manner with said heating means of said plurality of heating means (14, 15, 16, 17) .

95. Apparatus according to any one of claims 73 to 94, wherein said applying means comprises first applying means arranged for applying a photocatalytic solution to said semifinished products (2) to generate layer means (200) on said semifinished products (2) .

96. Apparatus according to claim 95, wherein said heating means comprises first heating means arranged for heating said photocatalytic solution of said layer means (200) on said semifinished products (2) .

97. Apparatus according to any one of claims 73 to 96, wherein said applying means comprises further applying means arranged for applying a photocatalytic solution to said semifinished products (2) to generate further layer means (201) on said semifinished products (2) .

98. Apparatus according to claim 97, wherein said heating means comprises further heating means arranged for heating said photocatalytic solution of said further layer means (201) on said semifinished products (2) .

99. Apparatus according to any one of claims 74 to 98, wherein said applying means comprises still further applying means arranged for applying a photocatalytic solution to said semifinished products (2) to generate still further layer means (202) on said semifinished products (2) .

100. Apparatus according to claim 99, wherein said heating means comprises still further heating means arranged for heating said photocatalytic solution of said still further layer means (202) on said semifinished products

(2) .

101. Apparatus according to any one of claims 73 to 100, wherein said applying means (8, 10, 11, 12, 13; 8, 50) comprises an application nozzle (30) for applying said solution.

102. Apparatus according to any one of claims 73 to 101, wherein said applying means (8, 10, 11, 12, 13; 8, 50) comprises a supplying nozzle (30) having adjustable dimensions (D) for applying said solution.

103. Apparatus according to any one of claims 73 to 102, and further comprising solution feeding means (20, 20' , 21) , for feeding said solution to said applying means (8, 10, 11, 12, 13; 8, 50) .

104. Apparatus according to any one of claims 73 to 103, and further comprising further controlling means (26, 27, 28, 29) arranged for controlling the position of said applying means (8, 10, 11, 12, 13; 8, 50) .

105. Apparatus according to claim 101, wherein said further controlling means comprises optical sensors (27, 28, 29) .

106. Apparatus according to claim 104, or 105, wherein said further controlling means comprises third controlling means for controlling the position of said applying means (8, 10, 11, 12, 13; 8, 50) in a desired direction.

107. Apparatus according to claim 106, wherein said further controlling means comprises fourth controlling means for controlling the position of said applying means (8,

10, 11, 12, 13; 8, 50) in a further desired direction.

108. Apparatus according to claim 106, or 107, wherein said further controlling means comprises still further controlling means for controlling the volume of the jet of solution dispensed by said applying means (8, 10,

11, 12, 13; 8, 50) .

109. Apparatus according to any one of claims 73 to 108, and further comprising further inspection means (29) arranged for inspecting the operation of said applying means (8) .

110. Apparatus according to claim 109, wherein said further inspection means comprises optical sensors (29) .

111. Apparatus according to any one of claims 73 to 110. and further comprising moving means arranged for moving said applying means (8, 10, 11, 12, 13; 8, 50) in a desired direction.

112. Apparatus according to claim 111, and further comprising further moving means arranged for moving said applying means (8, 10, 11, 12, 13; 8, 50) in a further desired direction that is different from said desired direction.

113. Apparatus according to any one of claims 73 to 112, and further comprising further locking means arranged for locking said applying means (8, 10, 11, 12, 13; 8, 50) in a desired application position.

114. Apparatus according to any one of claims 73 to 113, and further comprising recycling means (31) arranged for recycling the excess dispensed solution.

115. Apparatus according to any one of claims 73 to 114 and further comprising preheating means positioned upstream of said applying means and arranged for heating said semifinished products (2) .

116. Apparatus according to any one of claims 73 to 115, and further comprising tensioning means for maintaining in tension said semifinished products (2) .

117. Method for treating semifinished products (2) comprising footwear elements and/or materials suitable for being used to obtain footwear elements, comprising moving along a desired path (F) said semifinished products (2) and applying a solution (200, 201, 202) of photocatalytic material to said semifinished products

(2) during said moving.

118. Method according to claim 117, and further comprising heating said solution (200, 201, 202) for making the excess solvent evaporate during said moving.

119. Method according to claim 118, wherein there is provided moving heating means (9) of said solution (200, 201, 202) during said heating.

120. Method according to claim 118, or 119, wherein there is provided controlling the position of heating means (9) .

121. Method according to claim 120, wherein said controlling comprises controlling the position of said heating means (9) in a desired direction.

122. Method according to claim 120, or 121, wherein said controlling comprises further controlling the position of said heating means (9) in a further desired direction.

123. Method according to any one of claims 118 to 122, and further comprising inspecting the operation of said heating means (9) .

124. Method according to any one of claims 118 to 123, and further comprising displacing said heating means (9) in a desired direction.

125. Method according to claim 124, and further comprising further displacing said heating means (9) in a further desired direction that is different from said desired direction.

126. Method according to any one of claims 118 to 125, and further comprising locking said heating means (9) in a desired heating position.

127. Method according to any one of claims 118 to 126, wherein said heating comprises repeatedly heating said solution (200, 201, 202) of a photocatalytic material on said semifinished products (2).

128. Method according to any one of claims 117 to 127, wherein said applying comprises repeatedly applying said solution (200, 201, 202) of a photocatalytic material to said semifinished products (2) .

129. Method according to any one of claims 118 to 127, or according to claim 128 as appended to any one of claims 118 to 127, wherein said heating is provided after said applying.

130. Method according to any one of claims 118 to 127, or according to claim 128 as appended to any one of claims 118 to 127, or according to claim 129, wherein repeating said applying and said heating for a desired number of times in an alternating manner is provided.

131. Method according to any one of claims 118 to 127, or according to claim 128 as appended to any one of claims 118 to 127, or according to claim 129, wherein said applying comprises applying a photocatalytic solution on said semifinished products (2) to generate layer means (200) on said semifinished products (2) .

132. Method according to claim 131, wherein said heating comprises heating said photocatalytic solution of said layer means (200) on said semifinished products (2) .

133. Method according to claim 131, or 132, wherein said applying comprises further applying a photocatalytic solution on said semifinished products (2) to generate further layer means (201) on said semifinished products (2) .

134. Method according to claim 133, wherein said heating comprises further heating said photocatalytic solution of said further layer means (201) on said semifinished products (2) .

135. Method according to any one of claims 131 to 134, wherein said applying comprises still further applying a photocatalytic solution to said semifinished products (2) to generate still further layer means (202) on said semifinished products (2) .

136. Method according to claim 135, wherein said heating comprises still further heating said photocatalytic solution of said still further layer means (202) on said semifinished products (2) .

137. Method according to any one of claims 117 to 136, wherein said applying comprises immersing said semifinished products (2) in containing means (50) of a photocatalytic solution (200, 201, 202).

138. Method according to claim 137, and further comprising preheating said semifinished products (2) before immersing said semifinished products (2) in said photocatalytic solution.

139. Method according to claim 137, or 138, and further comprising drying said solution on said semifinished products (2) after said immersing.

140. Method according to any one of claims 117 to 139, wherein there is provided shifting applying means (8, 10, 11, 12, 13; 8, 50) for applying said solution during said applying.

141. Method according to any one of claims 117 to 140. wherein adjusting the dimensions (D) of a dispensing nozzle (30) for applying said solution is provided.

142. Method according to any one of claims 117 to 141, and further comprising feeding said solution to said applying means (8, 10, 11, 12, 13; 8, 50) .

143. Method according to any one of claims 117 to 142, and further comprising further controlling the position of said applying means (8, 10, 11, 12, 13; 8, 50) .

144. Method according to claim 143, wherein said further controlling comprises checking the position of said applying means (8, 10, 11, 12, 13; 8, 50) in a desired direction.

145. Method according to claim 144, wherein said further controlling comprises further checking the position of said applying means (8, 10, 11, 12, 13; 8, 50) in a further desired direction.

146. Method according to any one of claims 117 to 145, wherein adjusting the volume of the jet of supplied solution is provided.

147. Method according to any one of claims 117 to 146, and further comprising further inspecting said applying means (8, 10, 11, 12, 13; 8, 50) .

148. Method according to any one of claims 117 to 146, and further comprising shifting said applying means (8, 10, 11, 12, 13; 8, 50) in a desired direction.

149. Method according to claim 148 , and further comprising further shifting said applying means (8, 10, 11, 12, 13; 8, 50) in a further desired direction that is different from said desired direction.

150. Method according to any one of claims 117 to 149, and further comprising further locking said applying means (8, 10, 11, 12, 13; 8, 50) in a desired application position.

151. Method according to any one of claims 117 to 150, and further comprising recycling the solution dispensed in excess .

152. Method according to any one of claims 117 to 150, and further comprising preheating said semifinished products (2) before said applying.

153. Use of Titanium dioxide for treating semifinished products for obtaining semifinished products having photocatalytic properties.

154. Use of Titanium dioxide for treating semifinished products for obtaining semifinished products having antibacterial properties .

155. Use of Titanium dioxide for treating semifinished products for obtaining semifinished products having odour-eating properties.

156. Use of Titanium dioxide for treating semifinished products for obtaining semifinished products having anti-mould properties.

157. Use of Titanium dioxide for treating semifinished products for obtaining semifinished products having antifungal properties.

158. Use according to any one of claims 153 to 157 of Titanium dioxide in the form of modified Anatase peroxide and/or peroxytitanic acid colloidal liquid water solution.

159. Use according to any one of claims 153 to 158, of Titanium dioxide in the form of Rutile.

160. Use according to any one of claims 153 to 159, of a silica-based compound and/or colloidal silica, for obtaining semifinished products having photocatalytic properties.

161. Use according to any one of claims 153 to 160, of a primer for obtaining semifinished products having photocatalytic properties.

162. Use according to any one of claims 153 to 161, of Titanium dioxide in the form of Brookite for obtaining semifinished products having photocatalytic properties.

163. Use according to any one of claims 153 to 162, of surfactants for obtaining semifinished products having photocatalytic properties.

164. Use according to any one of claims 153 to 163, of additives for obtaining semifinished products having photocatalytic properties.

165. Use according to any one of claims 153 to 164, of gripping materials for obtaining semifinished products having photocatalytic properties.

166. Use according to any one of claims 153 to 165, of silver-based compounds (Ag) and/or of a derivative thereof, for obtaining semifinished products having photocatalytic properties.

167. Use according to any one of claims 153 to 166, of a silver salt, such as, for example, silver acetate (CH₃COOAg) for obtaining semifinished products having photocatalytic properties.

168. Use according to any one of claims 153 to 167, of copper (Cu) , and/or a derivative thereof, and/or copper-based compounds for obtaining semifinished products having photocatalytic properties,

169. Use according to any one of claims 153 to 168, of a component selected in a group comprising sodium hydroxide (NaOH) , lithium oxide (Li₂O) , sodium sulphite heptahydrate (Na₂S₂O₃^H₂O), sodium thiosulphate pentahydrate (Na₂SO₃* 5H₂O) for obtaining semifinished products having photocatalytic properties.

170. Use according to any one of claims 153 to 169, of Titanium dioxide as Anatase, or Anatase peroxide, in a percentage comprised between approximately 60% and approximately 95%, and/or Titanium dioxide in the form of Rutile and/or of peroxytitanic acid and/or of Brookite in a percentage comprised between approximately 40% and approximately 5%, for obtaining semifinished products having photocatalytic properties.

171. Use according to any one of claims 153 to 170, of Titanium dioxide as Anatase, or Anatase peroxide, in a percentage comprised between approximately 70% and approximately 90%, and/or Titanium dioxide in the form of Rutile and/or of peroxytitanic acid and/or of Brookite in a percentage comprised between approximately 30% and approximately 10%, for obtaining semifinished products having photocatalytic properties.

172. Use of a water solution in amorphous state comprising a percentage of Titanium dioxide as peroxytitanic acid comprised between approximately 0.5% to 9.70% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

173. Use of a water solution in amorphous state comprising a percentage of Titanium dioxide as peroxytitanic acid of approximately 0.85% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

174. Use of a water solution containing a percentage of silica gel comprised between approximately 0.05% and approximately 19.90% by weight, cationic surfactants in a percentage comprised between approximately 0.05% and approximately 5.00% by weight, acrylic resin in a percentage comprised between approximately 0.05% and approximately 9.00% by weight, sodium hydroxide NaOH in a percentage comprised between approximately 0.005% and approximately 5.00% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

175. Use of a water solution containing a percentage by weight of silica gel of approximately 7.50%, cationic surfactants of approximately 1.00%, NaOH of approximately 0.10%, acrylic resin of approximately 1,50%, and H₂O of 89.90%, for obtaining semifinished products having photocatalytic properties.

176. Use of a crystalline water solution containing a percentage of Titanium dioxide as modified Anatase peroxide comprised between approximately 0.5% and approximately 9.90% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

177. Use of a crystalline water solution containing a percentage of Titanium dioxide as modified Anatase peroxide of approximately 0.85% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

178. Use of a water solution containing a percentage by weight of Titanium dioxide of a mixture consisting of approximately 70% from a solution of modified Anatase peroxide and approximately 30% from peroxytitanic acid for obtaining semifinished products having photocatalytic properties.

179. Use of a water solution containing a percentage of Titanium dioxide comprised between approximately 0.05% and approximately 9.90% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

180. Use of a water solution containing a percentage of Titanium dioxide of approximately 0.85% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

181. Use of a water solution containing a percentage by- weight of Titanium dioxide of a mixture consisting of approximately 70% from a solution of modified Anatase peroxide and approximately 30% from peroxytitanic acid and silver acetate C₂H₃AgO₂ for obtaining semifinished products having photocatalytic properties.

182. Use of a water solution containing a percentage of Titanium dioxide comprised between approximately 0.05% and approximately 9.90% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

183. Use of a water solution containing a percentage of Titanium dioxide of approximately 0.85% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

184. Use of a water solution containing a percentage of Titanium dioxide of approximately 80% as Anatase and of approximately 20% as Rutile, comprised between approximately 0.05% to approximately 9.5% by weight, and H₂O for the remaining part for obtaining semifinished products having photocatalytic properties.

185. Use of a water solution containing a percentage of Titanium dioxide of approximately 3.0% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

186. Use of a water solution containing a percentage of approximately 80% Titanium dioxide as Anatase and approximately 20% as Rutile, comprised between approximately 0.05% to approximately 9.5% by weight, and H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

187. Use of a water solution containing a percentage of Titanium dioxide in the form of Brookite comprised between approximately 0.01% and approximately 9.5% by weight, a percentage comprised between approximately 0.001% and approximately 5.0% by weight of a surfactant, for example [Ci₄H₂₂O(C₂H₄O)_n], a percentage comprised between approximately 0.009% and approximately 0.1% by weight of silver acetate C₂H₃AgO₂, H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

188. Use of a water solution containing a percentage of Titanium dioxide in the form of Brookite of approximately 0.5% by weight, a percentage comprised between approximately 0.001% and approximately 5.0% by weight of a surfactant, for example [Ci₄H₂₂O(C₂H₄O)_n], a percentage comprised between approximately 0.009% and approximately 0.1% by weight of silver acetate C₂H₃AgO₂, H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties.

189. Use of a water solution containing a percentage of Titanium dioxide in the form of Anatase of approximately 1.49% by weight, approximately 0.91% by weight of colloidal silica SiO₂, approximately 0.05% by weight of sodium hydroxide NaOH, approximately 0.13% by weight of lithium oxide Li₂O, approximately 0.015% by weight of sodium sulphite Na₂SO₃* 7H₂O, approximately 0.03% by weight of sodium thiosulphate Na₂S₂O₃* 5H₂O, approximately 0.005% by weight of silver acetate C₂H₃AgO₂, water H₂O for the remaining part, for obtaining semifinished products having photocatalytic properties .

190. Use of a water solution containing a percentage of Titanium dioxide in the form of Anatase comprised between approximately 1% and approximately 1.15% by weight, colloidal silica comprised between approximately 1,85% and approximately 2.05%, approximately 0.05%, sodium hydroxide NaOH, lithium oxide Li₂O comprised between approximately 0.20% and approximately 0.25%, sodium sulphite Na₂SO₃* 7H₂O between approximately 0.15% and approximately 0.20%, sodium thiosulphate Na₂S₂O₃*5H₂O between approximately 0.40% and approximately 0.45%, silver acetate C₂H₃AgO₂ between approximately 0.032% and approximately 0.040%, sodium sulphate NaSO₄ between approximately 0.25% and approximately 0.30%, water H₂O for the remaining part, approximately 97.37%, for obtaining semifinished products having photocatalytic properties. Use according to any one of claims 153 to 190, wherein said semifinished products comprise footwear and/or footwear elements and/or materials suitable for being used to obtain footwear elements and/or footwear.