ES2256891T3

Photocatalytic hydrophilic coating composition

Abstract

THE INVENTION REFERS TO A COMPOSITION THAT CAN HYDROFILIZE THE SURFACE OF A STRUCTURE TO PROVIDE AN ANTI-FLOOD PROPERTY TO THE SURFACE OF THE STRUCTURE. THE COMPOSITION TO HYDROFILIZE THE STRUCTURE SURFACE IS FORMED AT LEAST (A) PHOTOCATALITICAL PARTICLES OF A METALLIC OXIDE, (B) A CAPABLE PRECURSOR OF FORMING A SILICONE RESIN FILM OR A CAPECULAR CAPE OF FORMULATING A SILICONE AND (C) A SOLVENT, BEING THE TOTAL CONTENT OF THE PHOTOCATALITIC PARTICLE AND THE SOLID MATTER OF THE PRECURSOR FROM 0.01 TO 5% BY WEIGHT. THE HYDROPHILIC CAPACITY CAN BE SIMPLY PROVIDED BY APPLYING THE COMPOSITION ON A STRUCTURE AND DRYING OR HEATING THE COMPOSITION APPLIED TO THE STRUCTURE. THE THIN RESULTING HYDROPHILIC FILM IS TRANSPARENT, AND BY HENDE DOES NOT SACRIFY THE TRANSPARENCY OF A STRUCTURE THAT NEEDS TO BE TRANSPARENT. IN ADDITION, THE SURFACE OF A STRUCTURE WITH THE COMPOSITION CITED APPLIED TO THAT END HAS SUCH PROPERTY THAT THE WATER DROPS ADHERED TO THE SAME CAN BE REMOVED IMMEDIATELY BY EVAPORATION AND IT IS LESS LIKELY THAT THE SURFACE IS COMPOSED BY ONE SAME, YOU CAN EASILY RELEASE THE POLLUTANT OF THE SAME.

ES2256891T3, drawing sheet 1 — Sheet 1 of 6

Term

Term ended

Projected expiry passed 16 July 2017, 9.2 years ago.

27 claims: 1 independent, 26 dependent

1
ES 2 256 891 T3 REIVINDICACIONES 1. Una composición para formar sobre la superficie de un miembro una película que se hace hidrófila tras la exposición a la luz, comprendiendo dicha composición (a) partículas fotocatalíticas de un óxido metálico, (b) al menos un componente seleccionado entre el grupo constituido por partículas finas de sílice y un precursor capaz de formar una película de sílice, (c) un disolvente y (d) un tensioactivo en la que el contenido total de las partículas fotocatalíticas y las partículas finas de sílice o el peso, en términos de sílice, del precursor en la composición es 0,01 a 1% en peso.
2
La composición de acuerdo con la reivindicación 1, que, cuando se aplica a un elemento, tiene, tras, la aplicación de la luz sobre la superficie del elemento, una calidad hidrófila de no más de 10° en términos del ángulo de contacto de la superficie con agua.
3
La composición de acuerdo con la reivindicación 2, en la que el ángulo de contacto de la superficie con agua es 5°.
4
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 3, en la que el diámetro medio de la micela de las partículas fotocatalíticas es 100 nm o menos.
5
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 4, en la que las partículas fotocatalíticas están constituidas por la forma antasa de óxido de titanio.
6
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 5, que comprende además un material que tiene un índice de refracción de no más de 2.
7
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 6, en la que el disolvente es un alcohol.
8
La composición de acuerdo con la reivindicación 7, en la que el alcohol es un alcohol líquido que tiene un peso molecular de 60 a 300.
9
La composición de acuerdo con la reivindicación 8, en la que el alcohol es un alcohol líquido que tiene un peso molecular de 60 a 100.
10
La composición de acuerdo con la reivindicación 1, en la que el contenido del tensioactivo es menos que 10 partes en peso en base a una parte en peso de la partícula fotocatalítica.
11
La composición de acuerdo con la reivindicación 10, en la que el contenido del tensioactivo es 0,4 a 2 partes en peso en base a una parte en peso de la partícula fotocatalítica.
12
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 11, que comprende además un ácido.
13
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 12, en la que la composición comprende las partículas finas de sílice y el diámetro medio de partícula de las partículas finas de sílice está en el intervalo de 1 a 100 nm.
14
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 12, en la que la composición comprende las partículas finas de sílice y el diámetro medio de partícula de las partículas finas de sílice está en el intervalo de 5 a 50 nm.
15
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 12, en la que la composición comprende las partículas finas de sílice y el diámetro medio de partícula de las partículas finas de sílice está en el intervalo de 8 a 20 nm.
16
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 12, en la que el precursor de una película de sílice es un silicato representado por la siguiente fórmula de composición media SiX q O (4-q)/2 ES 2 256 891 T3 en la que X representa un grupo alcoxi o un átomo de halógeno y q es un número que satisface 0 < q < 4.
17
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 12, en la que el precursor de una película de sílice es un derivado de silano tetrafuncional, hidrolizable representado por la fórmula general:SiX4 en la que X representa un grupo alcoxi o un átomo de halógeno.
18
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 17, que comprende además un metal antibacteriano o un compuesto del mismo.
19
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 18, que comprende además al menos un metal seleccionado entre el grupo constituido por platino, paladio, rodio, rutenio, osmio, e iridio.
20
La composición de acuerdo con una cualquiera de las reivindicaciones 1 a 19, en la que el óxido fotocatalítico se selecciona entre el grupo constituido por la forma anatasa de óxido de titanio, forma rutilo de óxido de titanio, óxido de cinc, óxido de estaño, óxido férrico, trióxido de dibismuto, trióxido de tungsteno, y titanato de estroncio.
21
Uso de la composición se acuerdo con una cualquiera de las reivindicaciones 1 a 20 aplicada a la superficie de un elemento para impartir una propiedad antiempañado a la superficie del elemento.
22
Uso de la composición se acuerdo con una cualquiera de las reivindicaciones 1 a 20 aplicada a la superficie de un elemento en la forma de una película para prevenir que la superficie se empañe o se ponga opaca por agua condensada de humedad y/o gotas de agua.
23
Uso de la composición se acuerdo con una cualquiera de las reivindicaciones 1 a 20 aplicada a la superficie de un elemento en la forma de una película para permitir un contaminante adherido a la superficie se retire por lavado fácilmente con agua.
24
Una composición de aerosol que comprende la composición de acuerdo con una cualquiera de las reivindicaciones 1 a 20, y un propulsor.
25
Un procedimiento para hidrofilizar la superficie de un elemento que comprende las etapas de:aplicar la composición de acuerdo con una cualquiera de las reivindicaciones 1 a 20 sobre la superficie de un elemento;y secar o curar la composición.
26
El procedimiento de acuerdo con la reivindicación 25, en la que el elemento es transparente y el elemento así obtenido es también transparente.
27
Un elemento que tiene una superficie hidrofilizada, producida por el procedimiento de acuerdo con la reivindicación 25 ó 26.

Independent claims27

288 paragraphs in 18 sections, as filed

ES 2 256 891 T3

DESCRIPTION

Photocatalytic hydrophytic coating composition.

Background of the invention

The present invention relates to a composition which, when applied to the surface of an element, can greatly hydrophilize the surface of the element, and, furthermore, can maintain the hydrophilic quality. More particularly, the present invention relates to a composition that can greatly hydrophilize the surface of mirrors, glasses, lenses, and other elements to prevent fogging of the surface of articles or elements and the formation of water droplets on the surface. surface of the elements or to clean the surface of the elements or to accelerate the removal of water droplets from the surface of the elements by vaporization, therefore quickly drying the surface of the articles or elements.

Background technique

Windshields or glass for automobiles and other vehicles, glass for buildings, eyeglass lenses, and protective glass for various instrument panels, when exposed to cold weather, are often fogged up by moisture condensation. Also, bathroom or sink mirrors and eyeglass lenses are often fogged up by steam. Exposing the surface of an article to a temperature below the dew point of an atmosphere causes moisture in the atmosphere to condense on the surface of the article and water droplets develop, creating a haze on the surface of the article. When condensed water droplets are very small, their diameter being approximately half the wavelength of visible light, the water droplets scatter the light and the mirror becomes opaque, which also results in loss. visibility.

The further progress of moisture condensation therefore causes the condensed fine water droplets to coalesce and develop into larger discrete water droplets that produce the refraction of light at the interface of the water droplets and the surface of the item and at the interface of water droplets and air, causing clouding, haze, creation of a spot pattern or otherwise fogging on the surface of the item. Therefore, in the case of a transparent article, such as glass, an image seen through it is distorted, causing the vision through it to be reduced, while in the case of a mirror, a reflected image is distorted. .

Furthermore, exposure of vehicle windshields or glass, building glass, vehicle rear view mirrors, eyeglass lenses, and mask or helmet screens to rain or water spray would therefore cause a large number of discrete water droplets adhere to the surface causing haze, haze, patterning, or otherwise fogging on the surface, which, here again, results in loss of visibility.

Needless to say, "foggy or cloudy" has a great effect on the safety and effectiveness of various jobs. For example, fogging or clouding of vehicle windshields or glass and vehicle rear view mirrors in cold or rainy weather makes it difficult to secure the field of vision and is therefore detrimental to traffic safety for vehicles. . Fogging of endoscopic lenses, dental mirrors, and converging lenses for laser dental treatment equipment will be an obstacle to proper diagnosis, operation, and treatment. Fogging of instrument panel glass makes data reading difficult.

On the other hand, in the field of buildings and cladding, the pollution of the environment has posed a problem of pollution of exterior materials for buildings, outdoor buildings, and coatings provided on them. Airborne dust and particles settle on the roof and exterior wall of buildings in good weather. Upon exposure to rain, the reservoirs flow together with the rainwater and flow along the outer edges of the building. Also, in rainy weather, the suspended dust is carried away by the rain and flows onto the outer wall of the building surface and the outdoor building surface. As a result, the pollutant sticks together with the course of the rain. As the surface dries, dirt appears in a stripy pattern.

Combustion products, such as carbon black, municipal dust, and contaminants from inorganic materials, such as clay particles, constitute the dirt on the exterior material cladding of the building. This wide variety of contaminants is considered to make anti-fouling measurement difficult (Yoshinori Kitsutaka, “Gaiheki Shiage Zairyou No Osen No Sokushin Shiken Houhou (Accelerated Testing Method for Contamination of Finish material of Outer Wall)”, Journal of Structural and Construction Engineering (Transactions of AIJ), No. 404, October 1989, pp. 15-24).

The use of water repellent paint, such as polytetrafluoroethylene (PTFE), has hitherto been considered preferable to prevent the exterior of the building and the like from dirt. However, in recent years, making the coating surface hydrophilic as much as possible has been recognized as more effective for municipal dust that contains a large amount of a hydrophobic component (Kobunshi, Vol. 44, May 1995, p . 307). Accordingly, the cladding of buildings with a hydrophilic graft polymer has been proposed in a newspaper ("Japan Chemical Week", January 30, 1995). According to this report, the coating has a hydrophilicity of 30 to 40 ° in terms of the angle of its contact with water.

ES 2 256 891 T3

Inorganic powder typified by clay materials has a contact angle with water of 20 ° to 50 ° and therefore has an affinity for graft polymer which has a contact angle of 30 ° to 40 ° and is likely to adhere to the surface of the graft polymer. Therefore, it is considered that the coating of the graft polymer cannot satisfactorily prevent fouling with inorganic dust.

Summary of the invention

The present inventors have now found that a specific composition comprising photocatalytic particles of a metal oxide, when applied to the surface of an element, can easily and greatly hydrophilize the surface of the element and, at the same time, can maintain high hydrophilicity. The present invention has been made based on such a finding.

In accordance with the foregoing, an object of the present invention is to provide a composition that can impart an antifog property to the surface of an element.

Another object of the present invention is to provide a composition that can impart an antifog property to the surface of an element without sacrificing the transparency of the element.

Still another object of the present invention is to provide a composition which, when applied to the surface of an element, can impart the property, to the surface of the element, of accelerating the evaporation of water droplets adhering on the surface of the element to the element. dried.

A further object of the present invention is to provide a composition which, when applied to the surface of an element, can impart such a property, to the surface of the element, so that the surface of the element is less likely to get dirty, even when once dirty, it can be easily freed from the contaminant therein.

According to one aspect of the present invention, there is provided a composition for hydrophilizing the surface of an element, comprising at least (a) photocatalytic particles of a metal oxide (b) at least one selected from the group consisting of fine particles of silica, a precursor capable of forming a silicone resin film and a precursor capable of forming a silica film, and (c) a solvent, the total solid content of the photocatalytic particle and the silica fine particles or the precursor in the composition which is 0.01 to 5% by weight.

Brief description of the drawings

Fig. 1 is a diagram showing an embodiment of a preferred spray container to be filled with the composition of the present invention;

Fig. 2 is a diagram showing an embodiment of a preferred lid for the spray container shown in Fig. 1;

Fig. 3 is a diagram showing an embodiment of another preferred spray container to be filled with the composition of the present invention;

Fig. 4 is a diagram showing an embodiment of yet another preferred spray container to be filled with the composition of the present invention; Y

Fig. 5 (a) and (b) are diagrams showing embodiments of the sectional shape of a balloon constituting a spray container to be filled with the composition of the present invention;

Fig. 6 is a diagram showing a change in antifog property of a surface of a hydrophilic surface prepared in Example 4A as a function of UV irradiation time; Y

Fig. 7 is a diagram showing a change in antifog property of a surface of a hydrophilic surface prepared in Example B1 as a function of UV irradiation time.

ES 2 256 891 T3

Detailed description of the invention

Definition

The term "antifog" used in this specification broadly means the prevention of optical problems caused by fogging or clouding of a surface, by developing condensed water droplets produced on the surface, or by adhering water droplets to the surface. .

Hydrophilic surface

The composition of the present invention, when applied to the surface of an element, by a procedure described below, can hydrophilize the surface of the element. Preferably, the hydrophilized surface has water wettability such that the contact angle of the surface with water is not more than 10 °, preferably not more than 5 °.

Furthermore, the composition of the present invention has an advantage that the surface of the element can be highly hydrophilicized while maintaining transparency. That hydrophilic property, specifically an antifog property, can be imparted to elements, required to be transparent, described below without sacrificing transparency and appearance is a great advantage of the present invention. Another great advantage is that the impartation of hydrophilicity can be accomplished very simply by applying the composition of the present invention to the surface of an element and drying or heating the composition applied to the surface. In fact, it is expected that a variation in the thickness of the film or uneven application is created depending on the surface of the elements. However, according to the composition of the present invention, regulating the amount of the composition applied so as to provide a film thickness described below and selecting the procedure for applying the composition so as to provide a uniform film allows the above excellent hydrophilic surface to be made very simply.

In order to hydrophilize the element with the composition applied to it, the surface is irradiated with light. The hydrophilization phenomenon is considered to proceed through the following mechanism. However, it should be noted that the following mechanism is purely hypothetical and should not be construed as limiting the scope of the present invention. Upon application of light having energy greater than the energy range, from a photocatalyst, between the upper end of the valence band and the lower end of the conduction band to the photocatalyst results in the photoexcitation of electrons in the band of valence, creating conduction electrons and holes. Either or both function to impart polarity, probably one (electron removal property) to the surface of the photocatalyst. This allows water in an amount greater than the amount of water in equilibrium with the amount of water in equilibrium with the atmosphere to be chemoabsorbed on the surface. This in turn increases the surface free energy derived from hydrogen bonding, which results in the absorption and physical fixation of water molecules in an amount that corresponds to the increase in surface surface free energy. In general, when the surface free energy of one substance is close to that of another surface, these substances are likely to adhere to each other. Therefore, the surface with water molecules that are physically absorbed into it have good water wettability. this means that such a surface has been hydrophilized. Furthermore, it has been found that the degree of surface hydrophilization provided by the composition of the present invention does not depend on the thickness of the thin film provided by the composition of the present invention. It is already known that a photocatalyst has oxidative degradation activity and a thin film containing a photocatalyst has anti-fouling, antibacterial, and deodorant effects based on such activity. The present inventors have confirmed that this oxidative degradation activity depends on the thickness of the film containing the photocatalyst. Furthermore, the present inventors have confirmed that the hydrophilization derived from the composition of the present invention can be developed even in such a film thickness that the oxidation degradation activation is very low or absent. Furthermore, the present inventors have confirmed that, in such a small thickness, of the film provided by the composition of the present invention, which will not influence the transparency of a transparent element, the oxidative degradation activity is very limited or, in some cases , absent.

When the surface is hydrophilized, the hydrophilicity, even when placed in a dark place, can be maintained for several weeks.

In order to greatly hydrophilize the surface by photoexcitation of the photocatalyst, the irradiation intensity of the excitation light is preferably not less than 0.001 mW / cm2, more preferably not less than 0.01 mW / cm2, more preferably not less than 0.1 mW / cm2.

When the photocatalytic oxide is the anatase form of titanium oxide, rutile form of titanium oxide, zinc oxide, or strontium titanate, sunlight, or a room lamp, a fluorescent lamp, a mercury lamp, an incandescent lamp , a xenon lamp, a high pressure sodium lamp, a metal halide lamp, a BLB lamp, and the like can be suitably used as a light source by photoexcitation of the photocatalyst. On the other hand, the photocatalytic oxide is tin oxide, a bactericidal lamp, a BLB lamp and the like are suitably used.

ES 2 256 891 T3

The thickness of the surface layer formed on the surface of the element using the composition according to the present invention is preferably more than 0.4 pm, the development of haze derived from uneven reflection can be prevented, so that the surface layer it is substantially transparent. The thickness of the surface layer is more preferably not more than 0.2 µm from the viewpoint of effectively preventing color development of the surface layer derived from light interference. The smaller the thickness of the surface layer, the better the transparency of the surface layer and also the better the abrasion resistance.

According to a preferred embodiment of the present invention, the content of the photocatalyst in the surface layer thus formed is preferably about 1 x 10 7 to 1 x 10 3 g / cm2, more preferably about 5x10 7 to 5 x 10 4 g / cm2, more preferably about 1 x 10 6 to 1 x 10 4 g / cm2.

Even when moisture or vapor in the air condenses on the highly hydrophilized surface provided by the composition of the present invention, the condensed water is likely to form a uniform water film without forming discrete water droplets. Therefore, light scattering haze is unlikely to be created on the surface of the element. Similarly, exposing glass, vehicle rear view mirrors, eyeglass lenses, and screens or helmets to rain or a water spray does not result in the formation of discrete water droplets that obstruct vision, because the Water droplets adhering to the surface of these articles spread out in a uniform film of water. This allows a high level of vision and visibility to be ensured, which in turn ensures traffic safety for vehicles and improves the efficiency of various jobs and activities.

In addition, both types of pollutants, specifically, hydrophobic pollutants including municipal dust, combustion products, such as carbon black contained in automobile exhaust gas, fats and oils, and components eluted from sealants, and pollutants from inorganic clay materials, they are less likely to adhere to the highly hydrophilic surface provided by the composition of the present invention and, even when adhered to, It can be easily washed by rain water or washed with water.

Furthermore, the highly hydrophilicized surface provided by the composition of the present invention allows adhering water droplets to spread over the surface, accelerating the removal of adhering water droplets by evaporation.

In addition, the highly hydrophilicized surface provided by the composition of the present invention has antistatic effect (effect of preserving dust deposition), has insulating effect, effect of preventing deposition of air bubbles under water, effect of improving biocompatibility.

When the composition of the present invention is expected to have an antifog effect, the element, to which the composition is applied, is generally transparent. The material for the element is not particularly limited, and examples thereof include glass and plastic. Specific examples of the items to which the composition can be applied include mirrors, such as vehicle rear view mirrors, bathroom mirrors, lavatory mirrors, dental mouth mirrors, reflective road mirrors; lenses, such as spectacle lenses, optical lenses, illumination lenses, semiconductor lenses, lenses for copying machines, vehicle rear view camera lenses; prisms; glass for buildings or observation; glass for vehicles, such as automobiles, rail vehicles, airplanes, ships, submarines, snowmobiles, cable tour nacelles, pleasure garden nacelles, and space aircraft; windshields for vehicles, airplanes, ships, submarines, snowmobiles, cable tour nacelles, pleasure garden nacelles and space aircraft; protective goggles, sports goggles, protective mask screens, sports mask screens, helmet screens, frozen food display glass, thermally held food display glass, such as Chinese muffin; covers for measuring instruments, covers for measuring instruments, lens covers for rear view camera for vehicles, converging lenses for laser dental treatment equipment, sensor covers for laser beam detection, such as sensors for vehicle shaft, covers for infrared sensors; camera filters, and films, sheets, stamps and the like for application on the surface of the above articles.

On the other hand, when the composition of the present invention is expected to have a surface cleaning effect, the material for the element is not particularly limited, and examples thereof include metals, ceramics, glasses, plastics, woods, etc. stones, cements, concretes, fibers, fabrics, and combinations of the above materials and laminates of the above materials. Specific examples of items to which the composition can be applied include building materials, building exteriors, building interiors, window frames, windshields, structural members, vehicle exterior and cladding, machinery exterior and articles, proof covers. of dust, traffic signs, various display devices, advertising towers or sign columns, noise barriers for roads, noise barriers for railways, bridges, exterior and guardrail cladding, interior facades and tunnel cladding, insulation, covers for solar cells, covers for solar energy collectors of solar water heaters, vinyl plastic greenhouses, covers for lighting of vehicles, homes, seats , bathtubs, water ponds, lighting equipment, lighting covers, kitchen utensils, cutlery, dishwashers, dish dryers, sinks, kitchen assortment, kitchen partitions, ventilation fans, and films, sheets, stamps and the like for the application on the surface of the previous articles.

ES 2 256 891 T3

Furthermore, when the composition of the present invention is expected to have the effect of accelerating the removal of water droplets by evaporation, the material for the element is not particularly limited, and examples thereof include metals, ceramics, glasses, plastics. , woods, stones, cements, concretes, fabrics, and combinations of the above materials and laminates of the above materials. Specific examples to which the composition can be applied include automobile bodies, windows, paved roads, and films, sheets, stamps and the like for application to the surface of the above articles.

Furthermore, when the composition of the present invention is expected to have an antistatic effect, the material for the element is not particularly limited, and examples thereof include metals, ceramics, glasses, plastics, woods, cements, concretes, fibers, etc. fabrics, and combinations of the above materials and laminates of the above materials. Specific examples of the elements to which the composition can be applied include cathode ray tubes; magnetic engraving media, optical engraving media; photomagnetic recording media, audio tapes, video tapes; analogous records; pipes, components, exterior and coating of household electrical appliances of office automatic equipment; Construction materials; exterior of buildings; interior of buildings; windowframes; windshield; structural elements; exterior and coating of vehicles; exterior of machinery and articles; dustproof covers and coating; and films, sheets, stamps and the like for application on the surface of Leo previous articles.

Composition of conversion to hydrophilic surfaces

The composition according to the present invention basically comprises (a) photocatalytic particles of a metal oxide (b) at least one selected from the group consisting of fine silica particles, a precursor capable of forming a silicone resin film and a precursor capable of forming a silica film, and (c) a solvent. Furthermore, the composition of the present invention may, if necessary, contain additional components.

Photocatalytic particles

The photocatalytic particles contained in the composition according to the present invention basically comprise a metal oxide. Specifically, in the present invention, the term "photocatalyst" used in this specification refers to a material which, when exposed to light (excitation light), has a high energy (ie, shorter wavelength) that the energy range between the conduction band and the valence band of the crystal, can cause excitation (photoexcitation) of electrons in the valence band that produces a conduction electron and a cavity. Photocatalytic oxides usable in this specification include, for example, the anatase form of titanium oxide, rutile form of titanium oxide, zinc oxide, tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide, and titanium titanate. strontium.

The mean micelle diameter of the photocatalytic particles is preferably no more than 100 nm. The upper limit of the mean micelle diameter is preferably about 20 nm, more preferably about 10 nm. The lower limit of the mean micelle diameter is preferably about 1 nm, more preferably about 3 nm. an average micelle diameter of the photocatalytic particles in the upper range makes it possible to hydrophilize the surface and prevent loss of transparency, of a surface with the composition applied to it, derived from the scattering of visible light caused by the particles.

The mean micelle diameter of the photocatalytic particles can be determined according to the Scherrer equation based on the integration width of a peak having an intensity of about 2 * = 25.3 ° by particle diffractometry.

Silica fine particles and silicone resin film precursor and silica film

The composition of the present invention contains fine silica particles. Silica can effectively immobilize photocatalytic particles on the surface of an element. According to a preferred embodiment of the present invention, the mean particle diameter of the silica fine particles is in the range of 1 to 100 nm, preferably 5 to 50 nm, more preferably 8 to 20 nm. The diameter of can be determined, for example, by the laser scattering method.

A preferred example of the precursor capable of forming a silica film that can be used in the composition of the present invention is a silicate represented by the following average composition formula:

SiXwhatOR(4-q) / 2 in which X represents an alkoxy group or a halogen atom and q is a number satisfying 0 <q <4.

ES 2 256 891 T3

Another preferred example of the precursor, of a silica coating, capable of forming a silica coating that can be used in the composition of the present invention is a hydrolyzable, tetrafunctional silane derivative represented by the general formula:

SiX4 wherein X represents an alkyl group or a halogen atom.

Specific examples of preferred hydrolyzable, tetrafunctional silane derivatives include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane, tetrachlorosilane, tetraobromosilane, silanol, and dimethoxydiethoxysilane.

Specific examples and preferred silicates include partial hydrolysates and dehydropolycondensation products of the hydrolyzable tetrafunctional silane derivatives.

A preferred example of the precursor, of a silicone coating, capable of forming a silicone film that can be used in the composition of the present invention is a siloxane represented by the formula of medium composition:

RpSIXqO (4_p_q) / 2 wherein R represents a member selected from the group consisting of a hydrogen atom and one or more organic groups;

X represents an alkoxy group or a halogen atom; yp is a number that satisfies 0 <p <2 and q is a number that satisfies 0 <q <4.

A preferred example of the precursor capable of forming a silicone film that can be used in the composition of the present invention is a hydrolyzable silane derivative represented by the general formula:

RpSlX4-p where R is as defined above;

X represents an alkoxy group or a halogen atom; and p is 1 or 2.

In this case, the organic group represented by R refers to an alkyl (more preferably an unsubstituted alkyl having 1 to 18 carbon atoms, more preferably an alkyl having 3 to 18 carbon atoms) or an aryl (preferably phenyl ).

Specific examples of silane derivatives, hydrolyzable include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, etiltributoxisilano, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimetoxidietoxisilano, dimetildipropoxisilano, dimetildibutoxixilano, dietildimetoxisilano, diethyldiethoxysilane, dietilldipropoxisilano, Diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldistoxysilane, phenylmethyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethylethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-acyltributoxysilanoxysilane.

The siloxane can be prepared by partial hydrolysis and dehydropolycondensation of the hydrolyzable silane derivative, or by dehydropolycondensation of a partial hydrolyzate of the hydrolyzable silane derivative with a partial hydrolyzate of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxy, or the like.

The silicone resin prepared by partial hydrolysis or dehydropolycondensation of the above precursor from the above precursor according to the following procedure is represented by the following average general formula:

RpYes(4-p) / 2 (I) in which R is as defined above; X is an alkoxy group or a halogen atom; Y

ES 2 256 891 T3 p is a number that satisfies 0 <p <2

The content of the precursor in the composition according to the present invention can be suitably determined. For example, in terms of the silica content on one part by weight of the photocatalytic particle, the upper limit of the precursor content is preferably 10 parts by weight, more preferably 5 parts by weight, most preferably 1 part by weight, and the Lower limit of the precursor content is preferably 0.05 part by weight, more preferably 0.1 part by weight, and most preferably 0.2 part by weight.

Solvent

The solvent contained in the composition of the present invention is not limited heretofore as it can stably disperse the photolytic particles and the precursor, the hydrophilized surface is finally provided. Examples of solvents usable in this specification include water, an organic solvent, and a mixed solvent composed of water and an organic solvent. Water, an alcohol, or a mixed solvent composed of water and an alcohol is particularly preferred.

The total weight of the photocatalytic particle and the weight of the silica fine particle or the weight, in terms of silica, of the precursor (this total content which is often referred to as a "solid content") is brought up to more than 0.01 to no more than 1% by weight in the composition of the present invention. The solid content can be determined simply as follows. The composition (weight: A) is heated at 400 to 500 ° C for three hours to remove the liquid component, and the weight of the residue (weight: B) is then measured, followed by calculating the solid content (%) according to with the following equation:

Solid content (%) = (B / A) x 100

When the solids content exceeds 5% by weight, the surface with the composition applied thereto in a disadvantageous manner has an appearance that suffers from haze development or has interference margins. The upper limit of the solid content is preferably not more than 1% by weight. When the solid content is less than 0.01% by weight, there is a possibility that a surface having hydrophilic quality cannot be formed efficiently. The lower limit of the solid content is preferably 0.05% by weight, more preferably 0.1% by weight. In the composition of the present invention, the amount of the solvent is determined so that the solid content of the photocatalytic particle and the precursor falls within the above range.

According to a preferred embodiment of the present invention, the use of an alcohol is preferred, which has a molecular weight of 60 to 300, preferably a molecular weight of 60 to 100 and is liquid at room temperature.

Examples of preferred alcohols usable in this specification include methanol, ethanol, n-propanol, isopropanol, t-butanol, isobutanol, n-butanol, 2-methylpropanol, pentanol, ethylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone , dipropylene glycol, propylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-propoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol, monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol and 2-butoxyethanol.

The addition of water as a solvent is often preferred from the viewpoint of accelerating the hydrolysis of the silica precursor. For example, when tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrapropoxysilane, tetrachlorosilane, or tetrabromosilane is used as the silica precursor, the presence of water accelerates hydrolysis upon application of the composition according to the present invention, as described. later. Other components

The composition according to the present invention may contain additional components in addition to the above components.

According to a preferred embodiment of the present invention, the composition according to the present invention contains a material having a refractive index of more than 2. The addition of the material having a refractive index of not more than 2 can offer a advantage so that the reflection of visible light on the surface with the composition applied to it can be effectively prevented.

Examples of materials having a refractive index or no more than 2 that can be added to the composition according to the present invention include silica (refractive index 1.5), tin oxide (refractive index 1.9), calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), carbonate of magnesium (refractive index 1.5), Strontium carbonate (refractive index 1.5), dolomite (refractive index 1.7), calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), alumina (refractive index 1.4), refraction 1.6), quartz sand (refractive index 1.6), zeolite (refractive index 1.5), montmorillonite (refractive index 1.5), kaolin (refractive index 1.6), sericite ( refractive index 1.6), ferric oxide (refractive index 1.8) and yttrium oxide (refractive index 1.9).

ES 2 256 891 T3

The composition of the present invention also comprises a surfactant. The addition of the surfactant allows a high hydrophilicity and antifog property to be imparted to the surface of a member even immediately after application of the composition to the member. In particular, when the composition according to the present invention contains an alcohol, the addition of the surfactant is preferred. In some cases, it takes several hours to achieve photohydrophilization of the surface with the composition of the present invention applied to it. In this case, when the alcohol derived from the composition of the present invention remains on the surface, the hydrophilization of the surface is often unsatisfactory until hydrophilization by the photocatalyst is achieved. The addition of the surfactant can advantageously hydrophilize the surface to a satisfactory degree, thereby imparting an antifog property, even immediately after application of the composition. Furthermore, the addition of the surfactant may offer an additional advantage so that the composition of the present invention can be applied uniformly to the surface of an element.

According to a preferred embodiment of the present invention, the amount of surfactant added is less than 10 parts by weight, more preferably about 0.1 to 2 parts by weight based on one part by weight of the photocatalytic particle.

Examples of surfactants that can be added to the composition of the present invention include anionic surfactants, such as ammonium polyoxyethylene alkylphenyl ether sulfonate, sodium polyoxyethylene alkylphenyl ether sulfonate, fatty acid sodium soaps, fatty acid potassium soaps, dissolthylsulfosuccinate sodium, alkyl sulfate, alkyl ether sulfate, sodium alkyl sulfate, polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, TEA salt of alkylsulfate, TEA salt of polyoxyethylene alkyl ether sulfate, sodium salt of 2-ethylhexylalkylsulfuric ester, sodium acylmethyltaurate, sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate, disodium lauryl sulfosuccinate, lauryl polyoxyethylene sulfuric acid, polyoxyethylene sulfuric acid, ethyl acetyl sulfate, polyoxyethylene sulfuric acid, polyoxyethylene sulfuric acid, polyoxyethylene sulfuric acid sulfa-FA ester sodium; Non-ionic surfactants, such as polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxylether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyethylene ether, polyoxyethylene polyethylene ether, stearate, polyoxyethylene alkylphenyl ether, polyoxyethylene oleate, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, polyether modified silicone, polyester modified silicone, sorbitan laurate, sorbitan stearate, sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan palmmitate, polyoxyethylene sorbitanyl ester glycol ester, polyoxyethylene glycine ester amide, lauric acid diethanolamide, oleic acid diethanolamide, oxyethylene dodecylamine, polyoxyethylene dodecylamine, polyoxyethylene alkylamine, polyoxyethylenectadecylamine, polyoxyethylene alkylpropylene diamine, polyoxyethylene oxypropylene block polymer, and polyoxidyethylene stearate; amphoteric surfactants, such as dimethyl alkyl betaine, alkylglycine, amide betaine, and imidazoline; and cationic surfactants, such as octadecyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dioleyl dimethyl ammonium chloride, 1-hydroxyethyl-2-alkylimidazoline quaternary salt, alkylisoquinolinium bromide, polymeric amine , octadecyl ammonium chloride, alkyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkylimidazoline quaternary salt, dialkyl dimethyl ammonium chloride, octadecylamine acetate, tetradecylamine acetate, alkylpropylenediamine, and didecyl dimethyl ammonium chloride.

According to a preferred embodiment of the present invention, the composition of the present invention contains an acid. The addition of the acid can increase the polarity of the surface with the composition of the present invention applied to it, allowing good hydrophilicity to be maintained even in a dark place.

Examples of acids that can be added to the composition of the present invention include acids that have a high ability to impart polarity to the surface such as nitric acid, sulfuric acid, hydrochloric acid, acetic acid, propionic acid, maleic acid, adipic acid. , fumaric acid, phthalic acid, valeric acid, lactic acid, butyric acid, citric acid, malic acid, picric acid, formic acid, carbonic acid, and phenol. Among others, citric acid, hydrochloric acid, sulfuric acid are particularly preferred.

According to another preferred embodiment of the present invention, the composition of the present invention contains a catalyst for the hydrolysis of silane. The presence of this catalyst accelerates the hydrolysis of the silane compound as the precursor after application, of the composition of the present invention, as described below. Examples of preferred catalysts include nitric acid, sulfuric acid, hydrochloric acid, acetic acid, propionic acid, maleic acid, atypic acid, fumaric acid, phthalic acid, valeric acid, lactic acid, butyric acid, citric acid, malic acid, picric acid. , formic acid, carbonic acid, and phenol, the above acids having a pH of 2 to 5.

According to a preferred embodiment of the present invention, the composition of the present invention, when the silica precursor is a silanol, contains a silanol polymerization curing catalyst. The presence of this catalyst can accelerate the silanol polymerization reaction after application of the composition of the present invention, in a manner as described below. Examples of preferred catalysts usable in this specification include aluminum compounds, such as aluminum chelate, aluminum acetyl acetonate, aluminum perchlorate, aluminum chloride, aluminum isobutoxide, and aluminum isopropoxide; titanium compounds, such as tetraisopropyl titanate, and tetrabutyl titanate; basic compounds, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, potassium acetate, potassium formate, potassium propionate, tetramethyl ammonium chloride, and tetramethylammonium hydroxide ; composed of

ES 2 256 891 T3 amine, such as n-hexylamine, tributylamine, diazabicycloundecene, ethylenediamine, hexanediamine, diethylenetriamine, tetraethylenepentamine, triethylenetetramine, ethanolamines, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, y- -aminopropylmethyldimethoxysilane, y- -aminoxysilane (y-aminopropylmethyldimethoxysilane, y- -aminoxysilano) (2-aminoethyl) -aminopropylmethyldimethoxysilane; tin compounds, such as tin acetylacetonate, and dibutyltin octylate; metal-containing compounds, such as cobalt octylate, cobalt acetylacetonate, and iron acetyl acetonate; and acidic compounds such as phosphoric acid, citric acid, phthalic acid, p-toluenesulfonic acid, and trichloroacetic acid.

According to a preferred embodiment of the present invention, the composition of the present invention contains a leveling agent so that when applied to the surface of the leveling agent it is particularly advantageous when the composition of the present invention is applied to an article. big. Examples of preferred leveling agents include diacetone alcohol, ethylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, dipropylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, propylene glycol monomethyl ether, 1-propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether.

According to a preferred embodiment, the composition of the present invention comprises an antibacterial metal (eg, silver, copper, or zinc) or a compound of the metal. The addition of the above metal allows the bacteria present on the surface of an element to be killed at the time of application of the composition of the present invention on the surface of the element. Furthermore, after application of the composition on the element, growth of organisms, such as fungi, algae, and moss, on the surface can be inhibited.

Furthermore, according to another preferred embodiment of the present invention, the composition of the present invention additionally comprises at least one metal from the platinum group selected from the group consisting of platinum, palladium, rhodium, ruthenium, osmium, and iridium. A surface having a metal oxide photocatalyst is known to have antifouling, antibacterial and deodorizing functions based on the oxidative degradation activity of the photocatalyst. The surface of an element with the composition of the present invention applied to it appears to maintain this activity. The above metal appears to enhance the oxidative degradation activity of the photocatalyst and improve the antibacterial property, deodorizing property, gas decomposing property, organic matter decomposing property and other surface properties.

The composition of the present invention, when stored in a tin container or a container constructed of a liner metal or when applied on a metallic element, is preferably weakly acidic, neutral or basic. In particular, when adding an acid as in the above embodiment, the addition of a pH adjuster is preferred.

Furthermore, the composition of the present invention may optionally contain an acid or a base in order to improve the dispersibility of the solid component (s) contained therein and to improve the storage stability of the composition. Furthermore, if necessary, it may further comprise pigments, dyes, storage stabilizers and the like.

Application of the composition of the present invention on the surface of the element

The composition of the present invention is applied onto the surface of an element to which the hydrophilic nature or antifog property is to be imparted, and the composition applied to the surface is then dried or cured to form a thin film.

As described above, preferably, the composition of the present invention is finally made into a thin film having a thickness of no more than µm, preferably no more than 0.2 µm, on an element. In order to form such a thin film, the composition of the present invention is applied to the surface of the limb in a coverage of preferably about 1 x 104 at 20 mg / cm2, more preferably about 5x10-4 at 1 mg / cm2.

The composition of the present invention can be applied to the surface of the element by any suitable method, and examples of suitable methods include spray coating, drip coating, flow coating, spin coating, roll coating, brush coating. , sponge coating.

The composition after application to the element surface is then dried or cured to form a thin film. The term "drying or curing" used in this specification means that the silica precursor or silicone precursor contained in the composition according to the present invention is converted to silica or silicone. Therefore, drying can be accomplished by either air drying or heat drying. Alternatively, ultraviolet irradiation or the like can be carried out to cause polymerization so far as the precursor is converted to silica or silicone.

In accordance with a preferred embodiment of the present invention, the composition of the present invention is supplied in such a state that it is loaded into a spray container, allowing users to properly apply the composition of the present invention to the surface of a desired item.

ES 2 256 891 T3

A suitable spray container for the composition of the present invention therein is shown in Figure 1. A container structure 1 is preferably made of aluminum which is light in weight, easy to work, and firm. However, duralumin, copper-aluminum alloy, titanium alloy, stainless steel, and the like can also be used.

When the composition of the present invention is acidic, an acid-resistant resin coating 2 is preferably provided from the viewpoint of avoiding direct contact of the metal container structure with the acidic composition. Acid resistant coatings usable in this specification include ABS resin coatings, polycarbonate, methylpentene resin, polyvinyl chloride, polypropylene, polyethylene, ethylene tetrafluoride resin, ethylene propylene fluoride, ethylene trifluoride chloride resin, resin vinylidene fluoride, alkoxy perfluoride resin, phenolic resin, epoxy resin, acrylic resin, polyether chloride, polysulfone, polystyrene, polyphenylene oxide, polyphenylene sulfide, polyimide, nylon, and ionomer. In the container shown in Figure 1, a removable lid shown in Figure 2 can be mounted on the top of the container. This cap comprises: a tube 3 for conducting the composition of the present invention to an expulsion section; an ejection nozzle 4; a stem 5 with the uppermost portion being located above a housing 12 so that it is pressed by a finger, a coil spring 6; a rubber 9; a mountain top 10; a packaging 11 provided in a part in which the mountainous cap 10 meshes the upper part of the structure of the container 1; and an accommodation 12. The stem 5 has in its lower recess to lead the composition of the present invention to the expulsion section. A communicating port 7 is provided above the ejection nozzle 4, and the communicating port 8 is provided towards a certain position of the rubber 9.

Therefore, before pressing the stem 5, the communication port 7 does not engage the ejection nozzle 4, and the communication port 8 is sealed by the rubber, thus preventing the composition from which it is being released. After pressing the stem 5, the communication port 8 is positioned in a space sandwiched between the stem 5 and the housing 12, and the composition that has been directed from the tube 3 into the space between the stem 5 and the housing 12 is led to the hole inside stem 5. At the same time, the communication station 7 engages the ejection nozzle 4, allowing the composition to be directed to the hole inside the stem 5 to be ejected through the ejection nozzle 4.

Preferably, the above acid resistant resin is used inside tube 3, stem 5, ejection nozzle 4, and housing 12.

Preferably, the rubber 9 is also an acid resistant rubber, that is, an ethylene rubber, a propylene rubber, or a silicone rubber or the like.

Preferably, the ejection nozzle 4 is slightly inclined upwards.

Furthermore, inside the stem 5, the hole in this part connected to the ejection nozzle can be provided with a cruciform slot or a spiral slot so that the composition can be easily directed into the nozzle.

In accordance with other embodiments of the spray container, the dual container structures shown in Figures 3 and 4 may be suitable.

In the construction shown in Figure 3, an inner container 13 is provided within the container shown in Figure 1, and the inner container is charged with a sample of coating liquid D11 and a propellant gas, such as nitrogen gas. , DEM, or LPG. This construction is preferred because even when the resin coating has small holes, the composition of the present invention does not come into contact with the structure of the metal container 1.

In the construction shown in Figure 4, a balloon container 14 having pressure resistance and good pressure transmission is provided, as an internal container, inside the container shown in Figure 1, and a hole is provided in the bottom of the container. This construction allows a gas and a liquid to be filled into separate respective sections of the container. For example, the balloon container 14 (section A in the drawing) can be filled with the composition of the present invention with a space (section B in the drawing) between the outer container and the balloon container that is being filled with gas. nitrogen. Therefore, undesirable phenomena can be prevented, for example, a reduction in the pressure inside the container due to a gradual dissolution of the gas in the liquid.

Nitrogen gas is filled through the hole in the bottom of the canister, and the canister hole is then sealed with a rubber stopper 15. This allows residual pressure after use to be released simply by removing the stopper 15, offering safety advantageously.

Suitable for constructing the balloon container 14 are polyethylene, polyvinyl chloride and the like having pressure resistance and good pressure transmission. The use of a sectional shape filled with irregularities, such as a petal-like sectional shape, as shown in Figures 5 (a) and 5 (b) is preferred from the viewpoint of improving pressure transmission.

ES 2 256 891 T3

Furthermore nitrogen gas, ether gases, such as dimethylene ether, and inert gases, such as argon and helium, can be used as the fill gas.

Examples

The present invention will be described in more detail with reference to the following examples, although it is not limited to these examples only.

The composition and acquisition means of titanium oxide soils used in the following examples are as follows.

Titanium dioxide soil ST-K01 - a composition composed of 8 parts by weight of titanium oxide particles (anatase form), 2 parts by weight of an alkyl silicate, 54.8 parts by weight of an aqueous acid solution nitric, 28 parts by weight of methanol, and 7.2 parts by weight of propanol; available from Ishihara Sangyo Kaisha Ltd.

Titanium oxide soil ST-K03 - a composition composed of 5 parts by weight of titanium oxide particles (anatase form), 5 parts by weight of an alkyl silicate, 54.8 parts by weight of an aqueous acid solution nitric, 28 parts by weight of methanol, and 28 parts by weight of propanol; available from Ishihara Sangyo Kaisha Ltd.

Colloidal solution of titanium oxide TA-15: a composition composed of 15 parts by weight of particles of titanium oxide (anatase form) and 85 parts by weight of an aqueous solution of nitric acid; available from Nissan Chemical Industries Ltd.

Example A1

Silica film precursor and amount of solvent

A colloidal solution of titanium oxide (ST-K01) was diluted 10 times, 100 times, or 1000 times with ethanol prepare samples A1, A2 and A3. The solid content of samples A1, A2 and A3 are 1% by weight, 0.1% by weight and 0.01% by weight, respectively.

These samples were allowed to stand for 3 days. As a result, no agglomeration was created.

Samples A1 through A3 were coated onto a 10 cm square soda-lime substrate, and the coatings were dried at room temperature for 18 hours.

As a result, for all samples, a transparent and uniform coating was formed. For the coating of sample A1, interference edges were also observed.

Subsequently, each coating was irradiated with a light source fluorescent lamp (BLB (black light blue), manufactured by Sankyo Denki) at an ultraviolet irradiation intensity of 0.25 mW / cm2 for an hour. Therefore, the antifog property of these coatings was evaluated. The evaluation criteria were as follows:

©: Breathing on the coated glass did not produce fogging.

Or: breathing on the coated glass produced a slight fogging with an image still clearly visible through the coated glass.

Δ: Breathing on the coated glass produced fogging to such a degree that an image would not be seen clearly through the coated glass although the fogging is not severe compared to that created on the substrate glass per se.

X: Breathing on the coated glass produced fogging comparable to that created on the substrate glass per

For the antifog property, samples A1 and A2 were evaluated as ©, and sample A3 as X.

For sample A1, the adhesion of the coating to the substrate and the peeling of the coating from the substrate were evaluated. In this case, for the evaluation of the adhesion of the coating to the substrate, Kimwipe impregnated with water was slid over the coating to determine the number of sliding operations necessary to cause the coating to the substrate was evaluated in terms of this number of operations of glide. On the other hand, for the evaluation of the peel of the coating on the substrate coating, a plastic remover was slid over the coating to determine the number of sliding operations necessary to cause the coating to completely peel off the substrate. The peeling of the coating from the substrate was evaluated in terms of this number of peeling operations. Each trial was repeated three times.

ES 2 256 891 T3

As a result, for the adhesion of the coating to the substrate, no peeling occurred after the sliding operation was repeated 20 times. On the other hand, for peeling the coating from the substrate, 2 to 3 sliding operations resulted in the complete peeling of the coating from the substrate.

Example 2

Copper addition

A solution of copper sulfate (100 µl) having a copper concentration of 1 g / liter was added to 10 g of a colloidal solution of titanium oxide (ST-K01), and the mixture was diluted 100 times with ethanol. The diluted liquid was allowed to stand for 3 days. As a result, no agglomeration was caused, in particular, it had good dispersion, suggesting that the addition of copper as an antibacterial metal to the coating liquid and the coating liquid can be used as in Example 1.

Example 3

Silica addition

A colloidal solution of titanium dioxide (TA-15) was diluted with ethanol to prepare a coating liquid having a concentration of titanium oxide particles of 0.5% by weight.

Separately, a colloidal solution of titanium dioxide (TA-15) was mixed with a colloidal solution of silica ("Glasca A", mean particle diameter: 10 nm, manufactured by Japan Synthetic Rubber Co., Ltd.), and the mixture was diluted with ethanol to prepare a coating liquid having a concentration of titanium oxide particles of 0.5% by weight and a concentration of silica particles of 0.5% by weight.

Each coating liquid was coated onto a 10 cm square soda-lime glass substrate, and the coated substrates were held at 50 ° C for one hour and allowed to stand for 15 minutes to cool the coated substrates, thereby preparing samples A4 and A5.

For samples A4 and A5, the coating was inspected. As a result, for sample A4, the coating reflected visible light and glare, while for sample A5, the coating did not substantially reflect visible light and had good permeability to visible light.

Furthermore, samples A4 and A5 were irradiated with light from a light source (BLB fluorescent lamp) at an ultraviolet irradiation intensity of 0.25 mW / cm2 for 2 hours. After this, the antifog property of the coating was evaluated. As a result, both samples had a good antifog property (©) in the antifog property evaluation according to Example A1.

The above results show that the addition of silica having a lower refractive index than titanium allows the resulting coating to have excellent anti-fog property while maintaining permeability of the surface to visible light.

Example A4

Addition of surfactant

A colloidal solution of titanium oxide (TA-15) was mixed with a colloidal solution of silica ("Glasca A"), and the mixture was diluted with ethanol to prepare a coating liquid having a concentration of titanium oxide particles. 0.5% by weight and a concentration of silica particles of 0.5% by weight.

A colloidal solution of titanium oxide (TA-15) was mixed with a colloidal solution of silica ("Glasca A"), and polyethylene glycol (3000 molecular weight) as a surfactant, and the mixture was diluted with ethanol to prepare a liquid of coating having a concentration of titanium oxide particles of 0.5% by weight, a concentration of silica particles of 0.5% by weight, and a concentration of polyethylene glycol of 0.2% by weight.

A colloidal solution of titanium oxide (TA-15) was mixed with a colloidal solution of silica ("Glasca A"), and a modified silicone (KF-351, polyether type, manufactured by The Shin-Etsu Chemical Co., Ltd. .), and the mixture was diluted with ethanol to prepare a coating liquid having a concentration of titanium oxide particles of 0.5% by weight, a concentration of silica particles of 0.5% by weight, and a modified silicone concentration of 0.2% by weight.

On the other hand, a solution of titanium oxide (TA-15) was mixed with a solution of silica ("Glasca A"), and a modified silicone (KF-945, polyether type, manufactured by The Shin-Etsu Chemical Co. , Ltd.), and the mixture was diluted with ethanol to prepare a coating liquid having a concentration of titanium oxide particles of 0.5% by weight, a concentration of silica particles of 0.5% by weight , and a modified silicone concentration of 0.2% by weight.

ES 2 256 891 T3

Each coating liquid was coated on a 10 cm square soda-lime substrate, and the coated substrates were kept at 5 ° C for one hour and allowed to stand for 15 minutes to cool the coated substrates, thereby preparing the samples A6 and A9.

Samples A6 to A9 were irradiated with light from a light source (BLB fluorescent lamp) at an ultraviolet irradiation intensity of 0.25 mW / cm2 to determine a change in antifog property of the coating as a function of light irradiation time. The results are shown in figure 6.

Specifically, for sample A6, a good antifog property (©) developed after irradiation for 2 hours. On the other hand, the irradiation time taken to develop a good antifog property (©) was three hours for sample A7, 4 hours for sample A8, and not less than 20 hours for sample A9, indicating that the addition of a Surfactant having higher hydrophobic site influence requires a longer UV irradiation time to develop an antifog property.

Example B1

Amount of surfactant

A solution of titanium oxide (TA-15), a colloidal solution of silica ("Glasca A"), a nonionic surfactant comprising a polyoxyethylene p-alkylphenyl ether (Penerole, NP-95, manufactured by Matsumoto Yushi), and Ethanol were mixed together to prepare a coating liquid samples B1 to B4 composed of titanium oxide particles, and a surfactant dispersed in a solvent.

TABLE 1

<td>Samples</td><td>Titanium oxide (parts by weight)</td><td>Silica particles (parts by weight)</td><td>Surfactant (parts by weight)</td>

Each of the coating liquid samples B1 to B4 was coated on a soda-lime glass substrate, and the coating was dried followed by irradiation with light from an ultraviolet light source, BLB fluorescent lamp (black light blue), (manufactured by Sankyo Denki) at an ultraviolet radiation intensity of 0.25 mW / cm2 to determine a change in antifog property of the coating as a function of light irradiation time.

The results are shown in Figure 7. Additionally, the antifog property was evaluated according to the same criteria as used in Example A1.

As shown in figure 7, despite the ultraviolet irradiation per se it only showed an anti-fogging property evaluated as X, while, 50 hours after the start of the ultraviolet irradiation, all the samples prepared by coating samples B1 to B4 of Coating liquid on the substrate glass surface exhibited good anti-fogging property (©).

The sample prepared by coating the coating liquid sample B1 did not show any anti-fogging property at all before UV irradiation, while the samples prepared by coating the coating liquid samples B2 to B4 showed a before and after anti-fogging property. of ultraviolet irradiation.

The reason that the sample prepared by coating the coating liquid sample B1 did not show the initial antifog property is believed to be that ethanol remained in the coating. The development of the anti-fogging property with increased irradiation time is considered to be attributable to the decomposition of ethanol by photoexcitation of the photocatalyst.

In contrast, for the samples prepared by the coating liquid samples B2 to B4 with a surfactant in it, an initial antifog property can be obtained by virtue of the presence of the surfactant in combination with ethanol. The antifog property is lost after a while and is restored again.

The reason for this is as follows. Photoexcitation of the photocatalyst results in the decomposition of not only the ethanol but also the surfactant to provide an intermediate, in the course of decomposition, which causes the hydrophilicity to be lost, resulting in temporary loss of the anti-fogging property. . However, upon complete decomposition of the surfactant, the hydrophilicity is restored again, resulting in the reestablishment of the antifog property.

ES 2 256 891 T3

This demonstrates that the addition of a surfactant in addition to the photocatalytic titanium oxide, silica, and ethanol particles offers not only a permanent antifog property but also an initial antifog property.

The greater the amount of surfactant, the longer the temporary loss time of the anti-fogging property.

Specifically, for the sample prepared by coating sample B2 of coating liquid with the surfactant that is added thereto in an amount as small as 0.4 part by weight based on the particle weight of photocatalytic titanium oxide, the time lost was about 2 hours, and, for the sample prepared by coating sample B3 of coating liquid with the surfactant added to it in an amount of 1 part by weight, the lost time was approximately 5 hours, while for the sample prepared by coating the coating liquid sample B4 with the surfactant added thereto in an amount of 2 parts, the lost time was approximately 24 hours. In addition, for the sample prepared by coating the coating liquid sample with the surfactant added thereto in an amount of 10 parts by weight based on the weight of the photocatalytic titanium oxide particles, the temporary lost time of the antifog property was 200 hours or more.

The temporary downtime of the antifog property, for example, when the coating liquid is supplied in the form of an aerosol, is preferably 1 day or less. The amount of the surfactant added is preferably less than 10 parts by weight, more preferably not more than 2 parts by weight.

In addition, for substrate glass that was irradiated with BLB light for 50 hours and samples prepared by coating samples B1 to B4 of coating liquid on the surface of the glass, the contact angle of the surface of the glass is measured. sample with water. The contact angle with water is measured, with a contact angle goniometer (CA-X150, manufactured by Kyowa Interface Science Co., Ltd.), 30 seconds after dripping a drop of water through a microsyringe onto the surface. of the sample.

As a result, the substrate glass had a contact angle of 30 °, while all the samples prepared by coating samples B1 to B4 of coating liquid on the surface of the substrate glass had a good contact angle with water, in particular, a contact angle of approximately 0 ° C.

Furthermore, the samples, prepared by coating samples B1 to B4 of coating liquid on the surface of the substrate glass, which has been evaluated for the contact angle of the same with water, was evaluated for the releasing ability of the stain of oil. Specifically, oleic acid was coated onto the surface of each sample, and each sample was then immersed in water that fills a water tank while keeping the sample surface horizontal.

As a result, the oleic acid became spherical, and the rubbing of the light caused the drop of oil to be released from the surface of the sample.

Example B2

Shine by adding cationic or non-ionic surfactant

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide ST-K03) (10% solid content by weight; the solute being composed of 5 parts by weight of titanium oxide (anatase form ) and 5 parts by weight of an alkyl silicate) were mixed together in a 1: 1 ratio, and the mixture was diluted 20 times with propanol to prepare a photocatalytic coating sample B5. Sorbitan monocaprylate (a nonionic surfactant) in an amount of 0.05% by weight (specifically, 0.325% by weight based on titanium oxide) was added to this sample B5 to prepare sample B6. Sorbitan monocaprylate in an amount of 0.1% by weight (specifically, 0.65% by weight based on titanium oxide) was added to sample B5 to prepare sample B7. A quaternary ammonium salt (a cationic surfactant) was added in an amount of 0.05% by weight to sample B5 to prepare sample B8. Furthermore, a quaternary ammonium salt was added in an amount of 0.1% by weight to sample B5 to prepare sample B9.

Samples B5 to B9 were coated onto a dark gray coated steel sheet, cleaned with ethanol, by flow coating, and the treated steel sheet was allowed to stand at room temperature for 18 hours (about 20 ° C). For this example, gloss was measured according to the procedure set forth in Japanese Industrial Standards (JIS) Z8741. As a result, the gloss was 94 for the coated steel sheet. On the other hand, it was 96 for sample B5, and the gloss for samples B6 to B9 with a surfactant added to it were respectively 102, 110, 106, and 112, indicating that the addition of a surfactant resulted in the development of brightness.

Samples B5 to B9 were then coated onto a slide, cleaned with ethanol, by flow coating, and the slides were allowed to stand at room temperature (about 20 ° C) for 18 hours. These samples were then irradiated with light from an ultraviolet light source fluorescent lamp (black light blue (BLB)), manufactured by Sankyo Denki) at an ultraviolet irradiation intensity of 0.5 mW / cm2 to determine a change in the antifog property of the coating as a function of the light irradiation time. What

ES 2 256 891 T3 result, samples B5 to B7 were found to have antifog property (©) from the beginning, sample B8 developed an antifog property evaluated as © 1.5 hours after the start of an ultraviolet irradiation evaluated as © 5 hours after the start of UV irradiation.

Example C1

Addition of anionic surfactant

Water (2450 parts by weight) and 0.025 parts by weight of an anionic surfactant (Rapisol A-80, manufactured by Nipón Oills & Fats Co., Ltd) were added to a colloidal solution of titanium oxide (ST-K01) to prepare a sample C1.

Water (2450 parts by weight) and 0.25 parts by weight of an anionic surfactant (Rapisol A-80, manufactured by Nipón Oills & Fats Co., Ltd) were added to a colloidal solution of titanium oxide (ST-K01) to prepare a C2 sample.

Samples C1 and C2 were allowed to stand for 3 days, during which time no agglomeration occurred.

Samples C1 and C2 were then coated onto a 10 cm square soda-lime glass plate by flow coating, and the coating was dried at room temperature for one hour to prepare samples C3 and C4.

For samples C3 and C4, neither haze development nor interference edges were observed, and a clear, uniform coating could be formed.

Then, the surface of samples C3 and C4 was irradiated with light from a light source fluorescent lamp (BLB (black light blue), manufactured by Sankyo Denki) at an ultraviolet irradiation intensity of 0.25 mW / cm2 for one day, followed by research on the contact angle of these samples with water, the anti-fogging property, and the removal of an oil stain with water. The contact angle with water was measured with a contact angle goniometer (CA-X150, manufactured by Kyowa Interface Science Co., Ltd.), 30 seconds after dripping a drop of water through a microsyringe onto the surface of the sample.

As a result, both C3 and C4 samples were highly hydrophilized at a water contact angle of about 0 ° C. For comparison, the contact angle of the soda-lime glass plate with water was measured and found to be 30 °.

The antifog property was evaluated according to the same criteria that were used in Example A1.

As a result, both samples C3 and C4 had good antifog property (©).

In addition, samples C3 and C4 were evaluated for oil spot release ability. Specifically, oleic acid was coated on the surface of each sample, and each sample was then immersed in water introduced into a water tank while keeping the sample surface horizontal.

As a result, for both samples, the oleic acid became spherical, and the rubbing of the light caused the oil drop to be released from the surface of the samples.

Example D1

Adding alcohol to a small object

A colloidal solution of titanium oxide (ST-K01) was diluted 25 times with 2-propanol to a sample of coating liquid D1.

The coating liquid was spray coated onto a 10 cm square soda-lime glass substrate, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, thereby preparing a D2 sample. .

On the other hand, a colloidal solution of titanium oxide (ST-K01) was diluted 25 times with ethanol to prepare a coating liquid sample D3.

The coating liquid was coated on a 10 cm square soda-lime glass substrate by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, thereby preparing a shows D4.

Subsequently, for samples D2 and D4, investigations were carried out on the contact angle with water and the appearance.

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The surface of samples D2 and D4 were irradiated with light from a light source fluorescent lamp (BLB (Black Light Blue), manufactured by Sankyo Denki) at an ultraviolet irradiation intensity of 0.25 mW / cm2 for 24 hours. After irradiation, the contact angle of these samples was measured with a contact angle goniometer (CA-X150, manufactured by Kyowa Interface Science Co., Ltd.), 30 seconds after a drop of water was dripped through a microsyringe on the surface of the sample.

As a result, both samples D2 and D4 were highly hydrophilicized at a contact angle thereof with water at 0 ° C. Furthermore, for samples D2 and D4, the coatings were transparent in appearance and free from lack of uniformity.

Example 2

Adding alcohol for a large item

Coating liquid sample D1 from Example D1 was coated onto a 50 cm square soda-lime glass substrate by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating. , therefore preparing a D5 sample.

On the other hand, a sample D3 of coating liquid from Example D1 was coated on a 50 cm square soda-lime glass substrate by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes. to cure the coating, thereby preparing a D6 sample.

For samples D5 and D6, investigations were conducted on the water contact angle and appearance.

The surface of samples D5 and D6 was irradiated with light from a light source fluorescent lamp (BLB (black light blue), manufactured by Sankyo Denki) at an ultraviolet irradiation intensity of 0.25 mW / cm2 for 24 hours. After irradiation, the contact angle of these samples was measured with a contact angle goniometer (CA-X150, manufactured by Kyowa Interface Science Co., Ltd.), 30 seconds after a drop of water was dripped through a microsyringe on the surface of the sample.

As a result, both samples D5 and D6 were highly hydrophilized up to a water contact angle of 0 ° C.

However, in this case, for sample D6 darkening was created at a position distant from the starting point of the flow coating, while for sample D5, the coating was transparent in appearance and free of non-uniformity.

Thus, this suggests that the use of propanol is preferable for application to a large size of a subject. Example D3

Adding alcohol for a large subject

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with 2-propanol to prepare a sample. coating liquid D7.

Coating liquid sample D7 was coated onto a 50 cm square soda-lime glass substrate by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing for hence a D8 sample.

Subsequently, for sample D8, investigations on water contact angle and appearance were carried out in the same way as in example D1.

As a result, sample D8 was found to be superhydrophilized to a contact angle with water at 0 ° C, and the coating was transparent in appearance and free from non-uniformity.

Example D4

Adding alcohol for a large subject

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with an 8: 2 mixture of 2- propanol and propylene glycol monopropyl ether to prepare a D9 coating liquid sample.

Coating liquid sample D9 was coated onto a 50 cm square soda-lime glass substrate by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing for hence a D10 sample.

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Subsequently, for sample D10, investigations on water contact angle and appearance were carried out in the same way as in example D1.

As a result, sample D10 was found to be superhydrophilic to a contact angle with water at 0 ° C, and the coating was transparent in appearance and free from non-uniformity.

Example D5

Adding alcohol for a large subject

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with a 9: 1 mixture of 2 -propanol and diacetone alcohol (4-hydroxy-4-methyl-pentanone) to prepare a sample of coating liquid D11 (pH 4).

Coating liquid sample D11 was coated onto a 50 cm square soda-lime glass substrate by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing by hence a D12 sample.

Subsequently, for sample D12, investigations on water contact angle and appearance were carried out in the same way as in example D1.

As a result, sample D10 was found to be superhydrophilic to a contact angle with water at 0 ° C, and the coating was transparent in appearance and free from non-uniformity.

Example D6

Application to automobile body: adding leveling agent

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with a 9: 1 mixture of 2 -ethanol and diacetone alcohol to prepare a sample of D13 coating liquid.

Coating liquid sample D13 was coated onto a hood (an engine hood) of an automobile, by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing by hence a D14 sample.

For sample D14, investigations on water contact angle and appearance were carried out in the same way as in example D1.

As a result, sample D14 was found to be superhydrophilized to a contact angle with water at 0 ° C. The coating surface was smooth, and the coating was transparent in appearance and free from non-uniformity.

Example D7

Application to automobile body: adding leveling agent

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with a mixture 8: 1: 1 of 2-ethanol, 2-propanol and diacetone alcohol to prepare a D15 coating liquid sample.

Coating liquid sample D15 was coated onto a hood (an engine hood) of an automobile, by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing by hence a D16 sample.

For sample D16, investigations on water contact angle and appearance were conducted in the same manner as in example D1.

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Example D8

Adding ethanol with leveling agent

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with an 8: 2 mixture of ethanol and propylene glycol monopropyl ether alcohol to prepare a D17 coating liquid sample.

Coating liquid sample D17 was coated onto a hood (an engine hood) of an automobile, by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing by hence a D18 sample.

For sample D18, investigations on water contact angle and appearance were carried out in the same way as in example D1.

As a result, sample D18 was found to be superhydrophilized to a contact angle with water at 0 ° C. The coating surface was smooth, and the coating was transparent in appearance and free from non-uniformity.

Example D9

Adding ethanol with leveling agent

A colloidal solution of titanium oxide (ST-K01) and a colloidal solution of titanium oxide (ST-K03) were mixed together in a 1: 1 ratio, and the mixture was diluted 25 times with a 9: 1 mixture of ethanol. and butyl cellosolve (2-butoxy ethanol) to prepare a D19 coating liquid sample.

Coating liquid sample D19 was coated onto a hood (an engine hood) of an automobile, by flow coating, and the coating was dried at room temperature (20 ° C) for 20 minutes to cure the coating, preparing by hence a D20 sample.

For sample D20, investigations on water contact angle and appearance were carried out in the same way as in example D1.

Example D10

Aerosol composition

The coating liquid sample D11 prepared in Example D5 and a nitrogen gas were filled in a volume ratio of 6: 4 into an aerosol container shown in Figure 1. From this aerosol container, the coating liquid sample D11 The coating was sprayed onto a slide substrate and the coating was allowed to stand at room temperature for 30 minutes to prepare a D13 sample.

For sample D13, investigations on water contact angle and appearance were carried out in the same way as in example D1.

As a result, sample D13 was found to be superhydrophilized to a contact angle with water at 0 ° C. The coating surface was smooth, and the coating was transparent in appearance and free from non-uniformity.

Example E1

Solid content and coating transparency

A soda-lime glass sheet (dimension: 40 x 100 x 2 mm) was dipped into a solution prepared by diluting a colloidal solution of titanium oxide (ST-K01) with ethanol and dip-coated by lifting the soda glass sheet -cal at a rise speed of 34 cm / min. Dilution of the titanium oxide colloidal solution with ethanol was carried out for the following solid content. The coatings were then heated to 50 ° C or 150 ° C to prepare samples E1 to E8. For these samples, the haze was measured with an haze meter (Hazegardplus, manufactured by Gardener).

ES 2 256 891 T3

The results are summarized in the following table

<td>Samples</td><td>Solid content% by weight)</td><td>Heat treatment temp. (° C)</td><td>Opacity (%)</td>

Example E2

Solid content and coating hardness

Samples E9 to E16 were prepared in the same manner as Example E1, except that ST-K03 was used as the titanium oxide solution. These samples were subjected to a pencil hardness test in accordance with the procedure set forth in Japanese Industrial Standard (JIS) H8602. The results are summarized in the following table.

<td>Samples</td><td>Solid content% by weight)</td><td>Heat treatment temp. (° C)</td><td>Pencil hardness</td>

29 members in 19 offices

This recordMember, by publication datePriority claim9 more offices are in the list below

Priority claims14

Priority claims
Document	Office	Kind	Date
19960221641	Japan	–	1996-07-19
22164196	Japan	A	1996-07-19
19960266554	Japan	–	1996-08-31
26655496	Japan	A	1996-08-31
19960285796	Japan	–	1996-09-20
28579696	Japan	A	1996-09-20
19960355953	Japan	–	1996-12-24
35595396	Japan	A	1996-12-24
19970013048	Japan	–	1997-01-08
1304897	Japan	A	1997-01-08
19970055533	Japan	–	1997-02-24
5553397	Japan	A	1997-02-24
19970093232	Japan	–	1997-03-26
9323297	Japan	A	1997-03-26

Members29

Family members, oldest first
Document	Office	Kind
CA2260803A1	Canada	A1	1998-01-29
WO9803607A1	World Intellectual Property Organization (WIPO)	A1	1998-01-29
AU3461397A	Australia	A	1998-02-10
JPH1081840A	Japan	A	1998-03-31
ID18659A	Indonesia	A	1998-04-30
EP0913447A1	European Patent Office (EPO)	A1	1999-05-06
EP0913447A4	European Patent Office (EPO)	A4	1999-05-26
BR9710382A	Brazil	A	1999-08-17
CN1230207A	China	A	1999-09-29
IL127998D0	Israel	D0	1999-11-30
NZ333743A	New Zealand	A	2000-02-28
JP2000095969A	Japan	A	2000-04-04
AU720317B2	Australia	B2	2000-05-25
HK1022493A1	Hong Kong, China	A1	2000-08-11
JP3077199B2	Japan	B2	2000-08-14
KR20000067874A	Republic of Korea	A	2000-11-25
US6165256A	United States of America	A	2000-12-26
TW467943B	Taiwan Province of China	B	2001-12-11
CN1142991C	China	C	2004-03-24
KR100468029B1	Republic of Korea	B1	2005-01-24
MY120003A	Malaysia	A	2005-08-30
EP0913447B1	European Patent Office (EPO)	B1	2006-02-15
AT317884T	Austria	T	2006-03-15
ATE317884T1	Austria	T1	2006-03-15
DE69735268D1	Germany	D1	2006-04-20
DK0913447T3	Denmark	T3	2006-06-19
ES2256891T3This record	Spain	T3	2006-07-16
DE69735268T2	Germany	T2	2006-10-12
CA2260803C	Canada	C	2007-06-26

Photocatalytic hydrophilic coating composition

Abstract

Term

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DESCRIPTION

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TABLE 1

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Priority claims14

Members29

Numbers

Titles2

Classification