JP2007038119A - Method of forming catalyst layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming on a substrate a catalyst layer showing functions such as fouling prevention, antifungal, and odor eliminating exerting a decomposition or attachment prevention function of contaminants with heat regardless of the presence or absence of light. <P>SOLUTION: A catalyst contains at least one kind of elements selected from silicon, aluminium, titanium, tin, and zinc, and potassium. A coating agent containing the catalyst exerting an oxidizing and/or reducing function by the heat is applied on the substrate to form the catalyst layer containing the catalyst on the substrate. The coating agent may be also constituted by the catalyst, and at least one kind of binders selected from a binder resin, a hydrolytic condensation compound, a glaze, and a paint. Further, in such a coating agent, a proportion of the catalyst may be about 10-100 pts.wt. to 100 pts.wt. binder. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the present invention, regardless of the presence or absence of light, a catalyst layer exhibiting functions such as antifouling, antibacterial, and deodorization is formed on a substrate by exerting a function of decomposing or preventing adhesion of contaminants by heat. The present invention relates to a method, a substrate on which the catalyst layer is formed, and a method for suppressing or preventing contamination of the substrate.

  Various devices and parts used in the kitchen (for example, a glass top stove top plate, five virtues, hot water and cooling water piping systems, etc.) are in a state where various stains and bacteria are likely to adhere. For this reason, a method is known in which a layer having a photocatalytic function is formed on the surface of these devices and the like, and the photocatalyst is photoexcited to hydrophilize the surface of the layer to impart antifouling properties. However, in this method, the presence of light (mainly ultraviolet rays) is indispensable. Therefore, the cooking equipment and its parts mainly used indoors are in a state where the imparting of antifouling properties is easily influenced by the environment (weather, season, day and night, direction of the building, etc.). Further, in order to suppress the growth of bacteria, a chemical solution has been injected into the cooling water piping system.

  As a method for imparting antifouling properties regardless of such changes in environmental conditions, a method using a charge transfer catalyst is known. For example, in Japanese Patent No. 3514702 (Patent Document 1), molybdenum and / or tungsten as an electron donating element, aluminum as an electron accepting element, zirconium as an electron carrier element, platinum as an oxidation center element, A catalyst comprising a composite oxide crystal of palladium as a reducing center element, and containing a lithium oxide as an oxidation activator and an yttrium oxide as a reduction activator inside and outside the crystal, is antifouling. It has been disclosed that functions such as properties, antibacterial properties, and deodorizing properties can be imparted to a substrate.

Further research is desired on a method that can easily impart functions such as antifouling properties, antibacterial properties, and deodorizing properties to a substrate regardless of such changes in environmental conditions.
Japanese Patent No. 3514702 (claims, paragraph number [0010])

  Accordingly, an object of the present invention is to provide a method for forming a catalyst layer that can exhibit an antibacterial, deodorant, and antifouling action on a base material by exhibiting oxidation and / or reduction action by heat, and the catalyst layer is formed. The object is to provide a substrate (parts, equipment, etc.) and a method for suppressing or preventing contamination of the substrate.

  Another object of the present invention is to provide a method for forming a catalyst layer capable of efficiently suppressing (or preventing) contamination of a substrate even in a place where light is not likely to strike (or where light is difficult to act), and the catalyst layer. It is an object of the present invention to provide a substrate (parts, equipment, etc.) on which is formed, and a method for suppressing or preventing contamination of the substrate.

  Still another object of the present invention is to provide a method for forming a catalyst layer that can be easily removed even if it is a contaminant that has already adhered (for example, adhering dirt such as oil or seasoning in a stove), and this catalyst layer is formed. Another object of the present invention is to provide a method for suppressing or preventing contamination of a base material (parts, equipment, etc.) and a base material.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have formed a catalyst layer containing a catalyst composed of a specific component and capable of exhibiting an oxidizing and / or reducing action by heat on the substrate. Because it functions as a catalyst due to charge transfer, even in an environment where light is difficult to act, it exhibits a function of decomposing or preventing adhesion of pollutants, and it has antibacterial, deodorant, antifouling effects, etc. on the substrate. The inventors have found that it can be expressed efficiently, and completed the present invention.

  That is, in the present invention, a coating agent containing a catalyst that exhibits an oxidation and / or reduction action by heat is applied to a substrate (or on the substrate, the substrate surface), and a catalyst layer containing the catalyst is formed on the substrate. A method for forming a catalyst layer, wherein the catalyst is a catalyst containing at least one element selected from silicon, aluminum, titanium, tin, and zinc and at least potassium. The catalyst is, for example, in terms of atoms, silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) = 1 / 0.05 to 1 / 0.01 to 2.5 / 0.001 to 2/0. The catalyst may contain silicon, aluminum, titanium, tin, zinc, and potassium at a ratio of 003 to 0.3 / 0.003 to 0.3. The coating agent may be composed of a catalyst and a binder (for example, at least one binder selected from binder resins, hydrolytic condensable compounds, glazes, and paints). In the forming method, the ratio of the catalyst in the coating agent may be about 10 to 100 parts by weight with respect to 100 parts by weight of the binder.

  Since the catalyst or catalyst layer has an oxidation and / or reduction action regardless of the presence or absence of light, the formation method may form the catalyst layer on a substrate used indoors or under light shielding. . In particular, in the formation method, in order to further increase the activity of the catalyst, a catalyst layer may be formed in the vicinity of the heating source in the base material. For example, among the stove as the base material, the top plate of the stove The catalyst layer may be formed on at least one portion selected from a stove saucer (for example, a saucer around the burner or a burner (a juice saucer)) and a gotoku.

  The base material in which the catalyst layer was formed by the said method (formation method) is also contained in this invention.

  According to the forming method, the catalyst layer is formed on the base material, and the catalyst exhibits an oxidation and / or reduction action (oxidation-reduction activity) by heat, whereby the function of decomposing or preventing adhesion of contaminants (or (Suppression function) can be expressed, and contamination of the substrate can be suppressed or prevented. Therefore, the present invention includes a method of forming or forming the catalyst layer on a base material to suppress or prevent contamination of the base material.

  In the method for forming a catalyst layer of the present invention, a catalyst layer composed of specific components is formed on a substrate, so that it exhibits oxidation and / or reduction action by heat, and the substrate is subjected to antibacterial, deodorant, Dirty action can be expressed. Further, in the method of the present invention, since a catalyst that exhibits a catalytic action by heat is used, the contamination of the base material is efficiently suppressed even in a place where it is mainly difficult to hit light (or where light does not act easily) (or Prevention). Furthermore, in the present invention, since the catalyst layer having the function of decomposing the pollutants is formed in advance by heat, even if the pollutants have already adhered to the base material (for example, adhering dirt such as oil and seasonings on the stove). Easy to remove.

  In the method for forming a catalyst layer of the present invention, a coating agent containing a specific catalyst that exhibits oxidation and / or reduction action (catalysis) by heat is applied to a substrate, and the catalyst layer containing the catalyst (coating layer, coating) is applied. Film) is formed on the substrate.

[Coating agent]
(catalyst)
The catalyst may be a substance that can exhibit an oxidation and / or reduction action (catalytic action) by the action of heat. Such a catalyst can exhibit a function of decomposing or preventing adhesion of contaminants (or contaminating components) or an anti-adhesion function (or suppression function) on the substrate by exhibiting an oxidation and / or reduction action by heat.

  The catalyst may be a catalyst (charge transfer catalyst, charge transfer catalyst) that can be oxidized and / or reduced by charge transfer, as long as it can exhibit catalytic activity by heat. Such a charge transfer catalyst (inorganic charge transfer catalyst) includes, for example, an electron donor element, an electron acceptor element, an electron carrier element that promotes the transfer of electrons from the electron donor element to the electron acceptor element, You may comprise at least the reduction center element which performs a reduction reaction by the electron which moved to the electron-accepting element, and / or the oxidation center element which performs an oxidation reaction by the hole of the electron donor element generated by the movement of the electron. The catalyst may further contain, if necessary, an activator that activates the redox reaction (an oxidation activator that activates the oxidation reaction and / or a reduction activator that activates the reduction reaction). Good.

  The charge transfer catalyst may contain the elements (and activators) in the form of atoms or compounds (for example, oxides, salts, etc.). Usually, the electron donating element, the electron accepting element, the electron carrier element, the reduction center element and / or the oxidation center element may be included in the catalyst in the form of a composite (usually a double oxide). For example, the catalyst may be composed of a double oxide crystal containing each element and the activator contained inside and outside the crystal. The charge transfer catalyst may contain an element that does not participate in charge transfer (that is, an element having no electron donating function, electron accepting function, oxidation or reduction activation function, etc.). Such an element may be contained in the catalyst in the form of a compound (such as an oxide) as described above.

  Regarding the charge transfer catalyst, JP-A No. 2002-1121 specifically discloses the above-mentioned elements and metal elements that function as activators. For example, molybdenum, tungsten, nickel, and One or more elements selected from the group consisting of cobalt as an electron accepting element, one or more elements selected from the group consisting of aluminum, silicon, tin, titanium, and iron as zirconium, manganese, and vanadium as electron carrier elements One or more elements selected from the group consisting of: one or more elements selected from the group consisting of silver and platinum as oxidation center elements; and one or more elements selected from the group consisting of palladium and zinc as reduction center elements As an oxidation activator, elements of group IA and IIA (for example, lithium, beryllium) Oxide selected from the group consisting of yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, and platinum as a reduction activator. The oxides of the above elements are illustrated.

  In the present invention, the catalyst is at least one selected from silicon (or silicon atoms), aluminum (or aluminum atoms), titanium (or titanium atoms), tin (or tin atoms), and zinc (or zinc atoms). And a catalyst containing at least potassium (or elemental potassium or potassium atom). In this invention, the decomposition | disassembly or adhesion prevention function of a pollutant is efficiently provided to a base material by using the catalyst containing these specific elements (or atoms). These elements (or atoms) and potassium may have any function selected from an electron donor element, an electron acceptor element, an electron carrier element, a reduction center element and / or an oxidation center element, and an activator. It may be a component (element) that does not necessarily have these functions. Usually, the catalyst often contains at least silicon, aluminum, titanium, tin, zinc, and potassium. In particular, the catalyst contains silicon, aluminum, titanium, tin and zinc in the form of oxides (including double oxides and double oxide crystals) and potassium as a potassium compound [especially potassium oxide (double oxide). It may be contained in the form of

  In the catalyst, the ratio of each component is, for example, silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) = 1 / 0.01 to 1.5 / 0.01 to atomic (or element) conversion. 3 / 0.001 to 3 / 0.001 to 0.5 / 0.001 to 0.5, preferably 1 / 0.05 to 1 / 0.01 to 2.5 / 0.001 to 2/0. 003-0.3 / 0.003-0.3, more preferably 1 / 0.1-0.8 / 0.1 / 0.01-1.6 / 0.005-0.1 / 0 0.005 to 0.1, especially 1 / 0.1 to 0.7 / 0.5 to 1.8 / 0.3 to 1.5 / 0.006 to 0.08 / 0.006 to 0.08 It may be 1 / 0.2 to 0.6 / 1 to 1.6 / 0.8 to 1.4 / 0.008 to 0.05 / 0.008 to 0.05. Good.

  The catalyst used in the present invention may contain elements having various functions described in JP-A-2002-1121.

  In the coating agent, the shape of the catalyst is not particularly limited, but may be usually powder (or powder). The average particle size (average diameter) of such catalyst powder is, for example, 5 nm or more (for example, about 5 to 600 nm), preferably 10 nm or more (for example, about 10 to 300 nm), and more preferably about 10 to 100 nm. May be.

  The catalyst powder contains particles having a relatively small particle size (for example, particles of about 10 to 100 nm, preferably about 10 to 30 nm) from the viewpoint of efficiently exhibiting catalytic action on the surface of the catalyst layer. preferable. Therefore, the maximum particle diameter (maximum diameter) of the catalyst powder is, for example, 500 nm or less (for example, about 20 to 400 nm), preferably 300 nm or less (for example, about 30 to 250 nm), and more preferably 200 nm or less (for example, 50 to About 150 nm).

(binder)
Although the coating agent should just contain the said catalyst at least, Usually, in order to adhere the said catalyst with respect to a base material efficiently, you may contain the binder. The binder can be appropriately selected according to the type (or material) of the substrate, and various organic or inorganic binders such as resins (binder resins), hydrolytic condensable compounds (alkoxysilanes, etc.), glazes, paints, etc. Is mentioned. The binders may be used alone or in combination of two or more.

  In the coating agent, when a binder is used, the ratio of the catalyst is, for example, about 3 to 200 parts by weight, preferably about 5 to 150 parts by weight, and more preferably about 10 to 100 parts by weight with respect to 100 parts by weight of the binder. May be.

  The coating agent may contain a solvent according to the coating method. Solvents include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene), alcohols (methanol) , Alkanols such as ethanol and propanol), ethers (eg, chain ethers such as dimethyl ether and diethyl ether, cyclic ethers such as tetrahydrofuran), ketones (dialkyl ketones such as acetone and ethyl methyl ketone) ), Esters (for example, acetate esters such as methyl acetate, ethyl acetate, and butyl acetate), diols (alkane diols such as ethylene glycol and propylene glycol, polyoxyethylene glycol, etc.), cellosolves (methyl celloso) Bed, such as ethyl cellosolve), etc. carbitol (carbitol), and water. These solvents may be used alone or in combination of two or more.

  The coating agent may contain a conventional additive depending on the type of binder.

  The coating agent containing a binder can be prepared by mixing the catalyst and the binder (if necessary, other components according to the kind of the binder and further a solvent as necessary). Usually, the coating agent can be prepared by dispersing the catalyst in a binder (or a system containing a binder). For mixing (and dispersion), a conventional mixer or disperser may be used.

[Method for forming catalyst layer and method for suppressing contamination]
In the present invention, the catalyst layer containing the catalyst (coating layer) is formed on the substrate by applying (or coating) the coating agent to the substrate.

  The substrate is not particularly limited as long as the coating agent can be coated (applied), for example, a device [for example, a stove (gas stove, etc.), an electromagnetic cooker, a cooking device such as a range, a ventilator, a range hood, a refrigerator, etc. Kitchen equipment, cooking utensils such as pots, kettles, frying pans, etc.], piping [for example, piping for distributing water (cooling water, hot water, etc.)], daily necessities (for example, cups, dishes, etc.), building materials (walls or wall materials) Etc.).

  Moreover, the material of the part which coats the said coating agent among base materials can be suitably selected according to the form of the said coating agent, the kind of binder, etc., and any of metal, glass, resin, ceramic, fiber, wood, etc. There may be.

  In particular, in the present invention, since a catalyst that exhibits an oxidation and / or reduction action by heat is used, the coating layer may be formed on a substrate that is difficult to be exposed to light, for example, indoors or under light shielding. The contamination of the substrate can be efficiently suppressed or prevented. As the base material used indoors or under light shielding, among the above exemplified base materials, equipment used indoors or under light shielding, for example, equipment placed or installed indoors (for example, kitchen equipment such as a gas stove) ), Inner surfaces or inner walls of equipment (for example, inner surfaces of pipes (or inner walls), inner walls of ranges, etc.), indoor building materials (indoor wall materials, etc.), and the like. In particular, if a catalyst layer is formed on the stove (table stove, built-in stove, etc.), the part (location) where it is troublesome to clean and wipe off contaminants adhering to the inner surface of the piping, cleaning and careability are greatly simplified. And the commercial value of the substrate can be improved.

  In the coating method, in particular, a catalyst layer may be formed in the vicinity of the heating source in the substrate. Since the catalyst exerts an oxidation and / or reduction action by heat, when the catalyst layer is formed in the vicinity of a heating source, that is, in a place (or part) where large thermal energy is likely to act, The catalytic action of the catalyst can be further improved, and contamination of the substrate can be efficiently suppressed or prevented. As a specific mode, (i) a mode in which a catalyst layer is formed in the vicinity of the heating source in a base material (for example, a stove) provided with a heating source (for example, a stove top plate, a stove pan ( 5) or a saucer around the burner (juice saucer, grill, etc.), a mode in which a catalyst layer is formed in the vicinity of the burner of the stove such as a stove, etc.), (ii) in the vicinity of (or in the vicinity of) the heating source A mode in which a catalyst layer is formed in the vicinity of the heating source among the substrates to be used [for example, a catalyst layer is formed in a cooking utensil (or its outer surface) used in the vicinity of a burner of a stove such as a pan, a frying pan, a kettle, etc. Etc.] and the like.

  In particular, in the vicinity of the burner as the heating source among the stove as the base material (for example, the top plate of the stove, the stove pan, the virtues of the stove, etc.) This is a part that takes time to remove. Therefore, if a catalyst layer is formed in the vicinity of such a burner, contaminants can be removed efficiently. Note that the top plate of the stove (or its coating) may be made of any material such as glass, enamel and stainless steel.

  The method for applying the coating agent to the substrate is not particularly limited, and, for example, depending on the type of coating agent (type of binder, etc.) and the shape and material of the part to be coated, Spray), dipping, or the like, or a conventional coating method (for example, dip coating, spin coating, flow coating, spray coating, etc.) may be used.

  The application may be performed once, or may be performed a plurality of times as necessary to form a catalyst layer having a desired thickness. Moreover, you may perform a drying process to the base material after application | coating as needed at appropriate temperature (for example, 40-150 degreeC, Preferably about 60-120 degreeC).

  Heat treatment may be applied to efficiently adhere or fix the catalyst layer to the substrate surface. In the heat treatment, the heating temperature and the heating time can be appropriately selected according to the type of the binder and the substrate.

  The thickness (average thickness) of the catalyst layer formed on the substrate by the above method can be selected according to the type of the substrate, the content ratio of the catalyst in the catalyst layer, etc., for example, 1 μm to 5 mm, preferably 10 μm to 1 mm, More preferably, it may be about 50 to 500 μm.

  In the base material on which the catalyst layer is formed by the method of the present invention, the catalyst can exhibit an oxidizing and / or reducing action by heat, thereby exhibiting a function of decomposing or preventing adhesion (or suppressing function) of contaminants. The contaminant is not particularly limited as long as it is a component that adheres to the substrate (or the substrate surface) and contaminates the substrate. For example, an organic substance (for example, oil, seasoning, drug, etc. attached to the stove) ), Microorganisms (for example, bacteria such as Escherichia coli, Legionella, Salmonella, etc.). That is, the catalyst (or catalyst layer) only needs to have a function of decomposing attached contaminants (for example, organic substances) or preventing (or suppressing) the attachment of contaminants. By exhibiting the function, antifouling, antibacterial, deodorizing and the like can be expressed on the base material. In addition, although contaminants such as the organic substances (such as seasonings) are artificially attached contaminants, in the present invention, even if they adhere to the base material (catalyst layer), they can be removed very easily by wiping or the like. Is possible.

  Therefore, the present invention also includes a method of forming or forming the catalyst layer (a catalyst layer containing the catalyst) on a substrate to suppress or prevent contamination of the substrate. In order to exert the catalytic action of the catalyst, it is necessary to apply heat (or thermal energy) to the base material (or the catalyst layer). The heat energy may be about the energy that acts on the substrate at 40 ° C., preferably about 15 to 30 ° C., and therefore, an operation such as a new heating is not necessarily required to exert the catalytic action. That is, when the catalyst layer is formed on the substrate, the function of preventing the decomposition or adhesion of contaminants is exhibited at a normal environmental temperature (room temperature).

  In particular, in order to more efficiently suppress or prevent the contamination of the base material, the catalyst layer to which the contaminant is attached may be heat-treated. By the heat treatment, attached contaminants can be removed more efficiently. In the heat treatment, the heating temperature and the heating time can be appropriately selected according to the type and amount of contaminants attached to the substrate, the material of the substrate, the type of binder, and the like. The heat treatment can be performed by heating (or heating) the substrate directly or indirectly, for example, directly or indirectly by the heat from the heating source as described above. Can also be heated.

  Hereinafter, the formation method of a coating agent and a catalyst layer is explained in full detail regarding a typical binder.

(Coating agent containing binder resin and method for forming catalyst layer)
The binder resin is not particularly limited, and various resins (such as a thermoplastic resin and a thermosetting resin) can be used. Examples of the thermoplastic resin include olefin resins (for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer), and styrene resin. (Eg, polystyrene, AS resin, ABS resin, etc.), polyester resins (eg, polyalkylene arylates such as polyethylene terephthalate and polybutylene terephthalate, or copolyesters thereof), polycarbonate resins (eg, bisphenol A polycarbonate), acrylic Resin (polymethyl methacrylate, methyl methacrylate-styrene copolymer, etc.), halogen-containing vinyl resin (polyvinyl chloride, etc.), polyamide resin (polyamide 6, polyamide 66, polyamide) 10, polyamide 612, polyamide 11, polyamide 12, etc.), polyacetal resin, polysulfone resin, poly (thio) ether resin (polyphenylene oxide, polyphenylene sulfide, etc.), thermoplastic elastomer (for example, polyolefin thermoplastic elastomer, polystyrene) Based thermoplastic elastomers, polyvinyl chloride based thermoplastic elastomers, polyurethane based thermoplastic elastomers, polyester based thermoplastic elastomers, polyamide based thermoplastic resin elastomers, etc.).

  Examples of the thermosetting resin include phenol resin, furan resin, amino resin [urea resin, melamine resin, etc.], unsaturated polyester resin, diallyl phthalate resin, epoxy resin, vinyl ester resin, polyurethane resin, silicone resin, polyimide resin. Etc. can be exemplified. The thermosetting resin may be an initial condensate.

  These resins may be used alone or in combination of two or more, and may be a polymer alloy (polymer multicomponent system) composed of a plurality of resins.

  The coating agent containing the catalyst and the binder resin may be solid or liquid. Usually, such a coating agent is often composed of a catalyst, a binder resin, and a solvent. Examples of the solvent include those exemplified above.

  The coating agent containing the binder resin can be prepared by mixing the catalyst, the binder resin, and (if necessary, a solvent). For example, the binder resin is dissolved or dispersed in the solvent, and the resulting solution or dispersion is used. The catalyst may be prepared by dispersing. In addition, you may prepare a solution or a dispersion liquid, stirring using a stirrer etc.

  The ratio of the catalyst may be, for example, 5 to 150 parts by weight, preferably 10 to 100 parts by weight, and more preferably about 20 to 80 parts by weight with respect to 100 parts by weight of the binder resin. If a coating agent is comprised in such a ratio, a catalyst can be efficiently deposited and fixed on the substrate surface.

  For coating of a coating agent containing a binder resin, conventional coating methods such as roll coating method, dip coating method, bar coating method, nozzle coating method, die coating method, spray coating method, spin coating method, curtain coating method, Flow coating, screen printing, gravure printing, curved surface printing, etc. can be employed.

  After the coating, the catalyst layer can be usually formed on the substrate by removing (desolving) the solvent by drying at an appropriate temperature (for example, about 50 to 150 ° C., preferably about 80 to 120 ° C.).

(Method of forming coating agent and catalyst layer containing hydrolytic condensable compound)
Examples of the hydrolytic condensable compound include silicon alkoxides (alkoxysilanes), aluminum alkoxides (for example, tri-C _1-4 alkoxyaluminates such as trimethoxyaluminate), titanium alkoxides (for example, tetramethoxy). And di- to tetra-C _1-4 alkoxy titanates such as titanate, tetraethoxy titanate and tetrapropoxy titanate).

Preferred hydrolytic condensable compounds include alkoxysilanes. Examples of alkoxysilanes include dialkoxysilanes [eg, dialkyldiC _1-4 alkoxysilanes (eg, dimethyldimethoxysilane), diaryldiC _1-4 alkoxysilanes (eg, diphenyldimethoxysilane), and functional groups. Having di-C _1-4 alkoxysilane (for example, 3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinyldimethoxymethylsilane, 3- (meth) acryloxypropylmethyldimethoxysilane, etc.)], trialkoxy silanes [e.g., tri C _1-4 alkoxy silane (e.g., trimethoxysilane, etc.), alkyl tri C _1-4 alkoxy silane (e.g., methyl trimethoxy silane), Arirutori C _1-4 alkoxysilane (e.g., phenylene Such as trimethoxysilane), tri C _1-4 alkoxysilane having a functional group (e.g., 2-aminoethyl trimethoxy silane, 3-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, 3- (meth) acryloxy propyl trimethoxy Methoxysilane, etc.], tetraalkoxysilanes [eg, tetra C _1-4 alkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), etc., condensation resulting from condensation of these alkoxysilanes Products (partial condensates) or oligomers (eg, oligomers of tetraalkoxysilanes (eg, 2-10 mer)). The hydrolytic condensable compounds may be used alone or in combination of two or more.

  The coating agent containing a hydrolytic condensable compound forms a coating layer on the substrate surface by a sol-gel method by hydrolytic condensation. Therefore, in addition to the hydrolytic condensable compound, the coating agent usually contains other components [for example, water, a solvent for preparing a homogeneous coating solution (for example, alcohols such as methanol, ethanol, propanol, butanol). Glycols such as ethylene glycol; organic solvents such as ethylene oxide, triethanolamine and xylene), catalysts for promoting hydrolysis (for example, acid catalysts such as hydrochloric acid, sulfuric acid, nitric acid, and fluoric acid); base catalysts such as ammonia Etc.) and a stabilizer (eg, acetylacetone, acetone, ethyl acetate, etc.) for stabilizing (polymerization termination) the polycondensate may be included. These other components may be used alone or in combination of two or more. When such a component and the hydrolytic condensable compound are mixed, a polycondensate (precondensate) of the hydrolytic condensable compound is obtained as a sol solution by hydrolysis and condensation reaction of the hydrolytic condensable compound.

  The coating liquid can be prepared by mixing a catalyst, a hydrolytic condensable compound, and [usually other components (water, alcohols, acid catalyst, etc.)]. It may be prepared by mixing components (water, alcohols, acid catalyst, etc.) to prepare a sol solution containing a precondensate, and mixing (and dispersing) the sol solution and the catalyst. The sol solution and the catalyst may be mixed by mixing the sol solution and the catalyst with another solvent. In addition, mixing and dispersion | distribution of a sol solution and a catalyst are performed using a conventional mixer or disperser (for example, a stirrer, a magnetic stirrer, a paint shaker, a homogenizer, an ultrasonic homogenizer, a sand mill, a three roll, a kneader, etc.). It can be carried out. The mixing time can be appropriately adjusted according to the type of the mixer or disperser.

  The ratio of the catalyst may be, for example, 5 to 150 parts by weight, preferably 10 to 100 parts by weight, and more preferably about 20 to 80 parts by weight with respect to 100 parts by weight of the hydrolytic condensable compound. If a coating agent is comprised in such a ratio, a catalyst can be efficiently deposited and fixed on the substrate surface.

  As the coating method of the coating liquid, the same conventional method as described above can be used. Then, after coating, hydrolytic condensation proceeds at an appropriate temperature (for example, room temperature), and a catalyst layer containing a condensate of the hydrolytic condensable compound can be formed on the substrate. In addition, in order to accelerate | stimulate a hydrolysis condensation reaction, you may heat-process the board | substrate after coating. In the heat treatment, the heat treatment temperature may be, for example, about 80 to 800 ° C., preferably about 150 to 700 ° C., more preferably about 300 to 600 ° C., and the heating time may be, for example, 5 minutes or more (for example, 10 Minutes to 5 hours), preferably 20 minutes or more (for example, about 30 minutes to 3 hours).

(Coating agent containing glaze and method for forming catalyst layer)
A glaze is a glass component (or a composition thereof) used to form a glass layer on the surface of ceramics, metal or the like. As the glass component can be appropriately selected depending on the type of substrate, for example, siliceous component (silicon dioxide), alumina component (Al ₂ O _3), calcium component (CaO, etc.), sodium component (Na ₂ O Etc.), boron components (such as B ₂ O ₃ ), potassium components (such as K ₂ O) and the like. The glaze may contain these glass components in the form of minerals containing glass components (eg, silica, feldspar, etc.). These glass components may be used alone or in combination of two or more. The glaze may be a colored glaze. The glaze may contain, in addition to the vitreous component, conventional components added to the glaze, such as clay, ammonium carbonate, an adhesive (such as cobalt oxide), and water.

  The glass component may be in the form of powder or frit. Usually, when enamel coating is applied to the base material (for example, the top plate of a stove, the virtues of a stove among the base materials), the glaze is a frit-like glass component. Often configured.

  The coating agent containing glaze can be prepared by mixing the catalyst and glaze (such as glass components and other components such as clay). Mixing can be carried out in accordance with a conventional glaze preparation method. For example, a coating liquid for enamel coating stirs a solvent (for example, water), the catalyst, and a fritted glaze using a stirrer or the like. However, it can be prepared by mixing.

  The ratio of the catalyst is, for example, 3 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the glaze (or the solid content of the glass component or glaze). There may be. If a coating agent is comprised in such a ratio, a catalyst can be efficiently deposited and fixed on the substrate surface.

  A coating method for the coating liquid containing the glaze is not particularly limited, and a conventional method can be used. Examples of the part of the base material to be coated with such a coating agent include metals such as steel (such as stainless steel), glass, and the like. Specific examples of the base material (or coating part of the base material) include, for example, A metal part of a cooking appliance (for example, a top plate of a stove, a virtues of a stove, etc.) can be used. Moreover, the coating liquid containing the glaze may be coated a plurality of times. For example, after forming the catalyst layer as a paste on the substrate, the catalyst layer may be further formed as a glaze. Moreover, after coating the coating agent containing a glaze, normally, a glaze is baked by baking processing (heat processing), and a catalyst layer is formed. In the firing treatment, the firing temperature (heating temperature) is, for example, 300 to 1500 ° C., preferably 500 to 1200 ° C., more preferably 700 to 1000 ° C. (for example, 770 to 850 ° C.), depending on the type of glass component. The heating time may be, for example, 10 seconds or longer (for example, 20 seconds to 1 hour), preferably 30 seconds or longer (for example, about 1 to 30 minutes). Prior to firing, the coated substrate may be dried (usually dehydrated). The dehydration may be performed for a predetermined time (for example, about 1 to 2 hours) under heating (for example, about 40 to 100 ° C.).

(Coating agent containing paint and method for forming catalyst layer)
Examples of the paint include oil-based paints (for example, oil-based paints, oil-based enamels), synthetic resin paints (for example, alkyd resin paints, amino resin paints, phenol resin paints, epoxy resin paints, polyurethane resin paints, unsaturated polyester resin paints). , Vinyl chloride-vinyl acetate copolymer resin paint, polyvinyl butyral resin paint, acrylic resin paint, etc.), cellulose derivative paint (eg, paint containing nitrocellulose as a coating component), alcoholic paint (eg, natural resin such as rosin) And a water-based paint (for example, an emulsion paint in which resin particles such as polyvinyl acetate, polystyrene, and styrene-butadiene copolymer are suspended in water). These paints may be used alone or in combination of two or more. The paint may be a powder paint.

  In addition to coating film forming components (drying oil, synthetic resin, natural resin, cellulose derivative, etc.), the paint is a conventional component added to the paint, for example, additives (pigments, plasticizers, pigment dispersants, Emulsifiers, thickeners, etc.), solvents (such as the solvents exemplified above) and the like.

  The ratio of the catalyst is, for example, 5 to 150 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the coating film forming component (or the solid content of the paint). It may be a degree. If a coating agent is comprised in such a ratio, a catalyst can be efficiently deposited and fixed on the substrate surface while maintaining the adhesion of the coating film to the substrate and the smoothness of the coating film.

  The coating agent containing the paint can be prepared by mixing the catalyst and the paint (coating film forming component, additive, solvent, etc.). The mixing may be performed by dispersing the catalyst using a dispersion such as a paint shaker or a mixer.

  In addition, as a coating method of the coating agent containing a paint, a conventional method (such as the method exemplified in the section of the binder resin) can be used. In addition, as a base material which coats a coating agent, metal plates, such as a steel plate (Dal steel plate etc.), etc. are mentioned, for example. The substrate after coating may be subjected to heat treatment in order to accelerate the curing of the paint and form a strong coating film.

  In the present invention, an antibacterial, deodorant, and antifouling effect can be imparted to a substrate regardless of the presence or absence of light by using a catalyst that exhibits an oxidizing and / or reducing action by heat. For example, when the coating method of the present invention is applied to an apparatus (for example, a gas stove) that easily adheres to pollutants and takes time to remove the pollutants, the catalyst is oxidized even after the pollutants are attached. In addition, due to the decomposition function associated with the reducing action, the contaminants can be easily removed by wiping, etc., and the contamination can be efficiently suppressed or prevented. Further, when the method of the present invention is applied to the inner surface of a pipe (pipe system) through which water (warm water, cooling water, etc.) flows, the oxidation / reduction action of the catalyst suppresses the adhesion of microorganisms (Legionella bacteria, etc.) to the pipe. It can prevent, and can give an excellent antibacterial action to the piping, and can greatly simplify the maintenance of the piping system.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
A catalyst powder containing silicon, aluminum, titanium, tin, zinc and potassium (silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) = 1 / 0.0. 4 / 1.4 / 1.1 / 0.01 / 0.01, powder having a particle size of about 10 to 100 nm) and 10 parts by weight of water are mixed using a stirrer, and a coating liquid (dispersion) is prepared. Prepared. This coating solution is applied by dripping onto the virtues, dried at 60 ° C for 1 hour, dehydrated, and heat-treated (fired) at 840 ° C for 3 minutes, to a test piece of the same material (low carbon steel) as the virtues. Enamel coating was applied.

  Further, a soil component (a mixture of a seasoning and an oil) expected to be used in Gotoku was dropped onto a test piece that had been subjected to enamel coating, and then heat treated at 250 ° C.

  Then, using an in-place type tension gauge (made by Oba Keiki Co., Ltd., trade name “AG3060”) with a metal spatula attached to the tip, the ease of removal of dirt components was evaluated. That is, when the load was gradually increased by bringing the metal spatula into contact with the dirt component adhering to the test piece, the dirt component was almost removed at 5N. FIG. 1 shows a photograph of a test piece before contact with a metal spatula (before evaluation) and a photograph of a test piece after removal of dirt components (after evaluation).

(Example 2)
80 parts by weight of a frit used for a container for a container and a catalyst powder containing silicon, aluminum, titanium, tin, zinc and potassium (silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) = 1/0. 4 / 1.4 / 1.1 / 0.01 / 0.01, powder having a particle size of about 10 to 100 nm) and 20 parts by weight are mixed with water using a stirrer, and a coating liquid (dispersion) is prepared. Prepared. This coating solution is applied by dripping onto the virtues, dried at 60 ° C for 1 hour, dehydrated, and heat-treated (fired) at 780 ° C for 3 minutes to form a test piece of the same material (low carbon steel) as the virtues. Enamel coating was applied.

  Then, in the same manner as in Example 1, the soil component was adhered to the test piece, heat-treated, and the ease of removal of the soil component was evaluated. The soil component was almost removed with a load of 5N.

(Comparative Example 1)
Except for not using catalyst powder, the dirt component was adhered under the same conditions as in Example 1, and the ease of removal of the dirt component was evaluated. The dirt component could not be removed even when the load was increased to 20N. It was. FIG. 2 also shows a photograph of the test piece before contact with the metal spatula (before evaluation) and a photograph of the test piece after the load of 20 N is applied (after evaluation).

(Example 3)
50 parts by weight of a tetraalkoxysilane condensate (manufactured by Nippon Soda Co., Ltd.) and catalyst powder containing silicon, aluminum, titanium, tin, zinc and potassium (silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) ) = 1 / 0.4 / 1.4 / 1.1 / 0.01 / 0.01, powder form having a particle size of about 10 to 100 nm) 50 parts by weight and water are mixed using a stirrer and coated. A liquid (dispersion) was prepared. This coating solution was applied to the top surface of the gas glass top stove and heat-treated at 500 ° C. for 1 hour to form a catalyst layer on the top surface.

  Further, after the soil component (mixture of seasoning and oil) was dropped onto the portion of the top plate where the catalyst layer was formed, the portion to which the soil component was adhered was heat-treated at a temperature of 250 ° C.

  And after leaving the heat-treated gas glass top stove in a dark place for one week and then wiping off the dirt component adhering to the top plate surface with a wet towel, the dirt could be easily removed.

(Comparative Example 2)
Except that the catalyst layer was not formed on the top surface, the soil component was adhered and heat-treated in the same manner as in Example 3, and after leaving it in the dark for one week, the stain was wiped off with a wet towel. In this case, the dirt could not be removed, and the dirt component remained on the surface.

Example 4
50 parts by weight of polycarbonate (manufactured by Teijin Chemicals Ltd., trade name “Panlite L-1225-L”) is dissolved in dichloromethane, and the resulting solution contains silicon, aluminum, titanium, tin, zinc and potassium. Catalyst powder (silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) = 1 / 0.4 / 1.4 / 1.1 / 0.01 / 0.01, powder form having a particle size of about 10 to 100 nm ) 50 parts by weight were mixed to prepare a coating liquid (dispersion). The coating liquid is applied to the inner surface (inner wall of the piping) of the cooling water piping system of the absorption chiller / heater of 100 refrigeration tons, and then dried to remove the solvent (desolvent), thereby removing the catalyst layer on the inner surface of the piping. Formed.

  After forming the catalyst layer, the absorption chiller / heater was operated, and water was circulated through the piping on which the catalyst layer was formed for one year. After observing the inner surface of the piping, slime formation on the inner surface of the piping was visually observed. It was not possible to confirm.

(Comparative Example 3)
Except that no catalyst layer was formed on the inner surface of the pipe, the absorption chiller / heater was operated for one year in the same manner as in Example 4 and the inner surface of the pipe was observed. Was formed.

FIG. 1 is a photograph of a test piece before contact with a metal spatula (before evaluation) and a photograph of a test piece after removal of dirt components (after evaluation) in Example 1. FIG. 2 is a photograph of a test piece before contact with a metal spatula (before evaluation) and a photograph of a test piece after a load of 20 N is applied (after evaluation) in Comparative Example 1.

Claims (9)

  A method of applying a coating agent containing a catalyst that exhibits oxidation and / or reduction action by heat to a substrate, and forming a catalyst layer containing the catalyst on the substrate, wherein the catalyst is silicon, aluminum, titanium, A method for forming a catalyst layer, which is a catalyst containing at least one element selected from tin and zinc and potassium.   The catalyst is, in terms of atoms, silicon / aluminum / titanium / tin / zinc / potassium (weight ratio) = 1 / 0.05 to 1 / 0.01 to 2.5 / 0.001 to 2 / 0.003 to 0. The process of claim 1 which is a catalyst comprising silicon, aluminum, titanium, tin, zinc, and potassium in a ratio of .3 / 0.003-0.3.   The method according to claim 1 or 2, wherein the coating agent comprises a catalyst and at least one binder selected from binder resins, hydrolytic condensable compounds, glazes and paints.   The method according to claim 3, wherein the ratio of the catalyst in the coating agent is 10 to 100 parts by weight with respect to 100 parts by weight of the binder.   The method of any one of Claims 1-4 which forms a catalyst layer in the base material used indoors or under light-shielding.   The method of any one of Claims 1-5 which forms a catalyst layer in the vicinity of a heat source among base materials.   The method according to any one of claims 1 to 6, wherein a catalyst layer is formed in at least one portion selected from a stove top plate, a stove pan and five virtues.   The base material with which the catalyst layer was formed by the method of any one of Claims 1-7. A method for suppressing or preventing contamination of a substrate by forming the catalyst layer according to any one of claims 1 to 7 on a substrate.