JP2022013196A - Deodorant antibacterial anti-fungal substance, deodorant antibacterial anti-fungal coating composition, and deodorant antibacterial anti-fungal coat - Google Patents

Abstract

To provide a substance capable of stably maintaining a deodorization effect for reducing efficiently, odor concentration, antibacterial and anti-fungal effects, and antiviral property, a coating composition using the same substance, and a coat formed of the coating composition.SOLUTION: A deodorant antibacterial anti-fungal substance has a porous coordination polymer formed of organic complex units and cross linkable organic compounds. In the porous coordination polymer, a three dimensional lattice group in which the organic complex units and the cross linkable organic compounds are alternately coupled in multi directions is provided. In the deodorant antibacterial anti-fungal substance, (1) the organic complex unit is formed of a compound having 1-6 divalent to tetravalent metal ions, and 2-4 carboxyl groups, (2) the cross linkable organic compound is an organic ligand having 2-4 nitrogen atoms in a structure, or having 1-2 carboxyl groups and 1-2 nitrogen atoms in the structure, and in addition, a photocatalytic metal oxide is carried in the three-dimensional lattice group.SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY The present invention effectively reduces the odor concentration of all unpleasant odor components such as rot of germs, propagation of mold, biological excrement, and unpleasant odor components such as cigarette smoke, exhaust gas, and volatile chemical substances. A deodorant antibacterial antibacterial substance that stably maintains the antibacterial and antifungal properties that suppress the growth of germs and molds that can cause stinks, and also has an antibacterial effect against virus infection, and this deodorant. The present invention relates to a deodorant antibacterial antifungal coating composition containing a sex antibacterial antifungal substance, and an invention of a deodorant antibacterial antifungal coating film containing the deodorant antibacterial antifungal substance. The deodorant antibacterial anti-mold material, the deodorant antibacterial anti-mold coating composition, and the deodorant anti-bacterial anti-mold coating film of the present invention include films, sheets, tapes, plastic molded products, metal plates, tarpaulins, mesh sheets, and the like. Used for materials such as synthetic leather, sail cloth, woven fabric, cloth, non-woven fabric, paper, etc., these deodorant antibacterial anti-mold substances or materials incidental with deodorant anti-bacterial anti-mold coating materials are ceiling films, space partitions, etc. , Roll-up lift sheet shutter, curtain, wallpaper, rug, cover, blind, air filter, medical non-woven protective clothing, non-woven mask, etc. are processed, factory, office, school, commercial facility, hospital, nursing facility, ceremony hall Widely used in garbage collection areas, public toilets, zoos, etc. In particular, a tarpaulin containing the deodorant antibacterial antifungal substance of the present invention, a woven fabric coated with a resin such as canvas, or a tarpaulin having a deodorant antibacterial antifungal coating film on the surface, and a resin coating such as canvas. The woven fabric can be suitable for medical temporary partitions, medical negative pressure tent shelters with an inflatable temporary membrane structure.

Previously, the applicant has a photocatalyst as an invention relating to a light-collecting heat-shielding film material which has a function of preventing soot and dust adhering stains which cause deterioration of the heat-shielding function and can efficiently maintain the heat-shielding function. We have proposed a film material (Patent Document 1) using a substance and a heat-controllable substance. In particular, as one of the aspects of the photocatalytic substance (as one of paragraphs [0063], the photocatalytic substance such as titanium oxide is used as silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite. , Silica alumina, calcium silicate, magnesium silicate aluminate, photocatalytic material as a means for supporting the photocatalytic substance on the inorganic porous fine particles such as silica soil, and as a means for supporting the photocatalytic substance on the inorganic porous fine particles. It is exemplified that a surface treatment applying a sol-gel thin film manufacturing process using a metal alcoholate containing the above is used. In the invention of the film material of Patent Document 1, the inorganic porous fine particles supporting the photocatalytic substance are used for the tent film material. It exists to prevent soot and dirt from adhering to dust, and has already carried a photocatalytic substance such as titanium oxide in the inorganic porous fine particles, and its adsorption capacity is not such that odor molecules can be effectively decomposed.

In addition, the applicant uses odor molecule-inactivating particles such as inorganic porous substances, oxidizing / reducing substances, and photocatalytic substances as the invention of the building curing mesh sheet having a deodorizing effect and a heat-shielding effect. The mesh sheet (Patent Document 2) was proposed. In particular, by using photocatalytic substances together with inorganic porous substances and oxidizing / reducing substances, as long as the building curing mesh sheet continues to be exposed to sunlight, the photocatalytic substances are activated, thereby adsorbing odor molecules. By constantly acting on inorganic porous substances and oxidizing / reducing substances coordinated by odor molecules, and by the action of this photocatalytic substance, odor molecules captured by physical adsorption or chemical coordination are decomposed and deodorized. It is disclosed in paragraph [0014] that inorganic porous substances and oxidizing / reducing substances can be reset to the initial state before adsorption and coordination, and new odor molecules can be captured, and as inorganic porous substances, It is disclosed in paragraph [0023] that activated charcoal, impregnated activated charcoal, white bamboo charcoal, activated white clay, zeolite, bentnite, sepiolite, silas, silica, silica-magnesia, molecular sieve and the like are used. However, in the mesh sheet of Patent Document 2, the decomposition efficiency of the odor molecules is inferior due to the separate presence of the inorganic porous substance that adsorbs the odor molecules and the photocatalytic substance that decomposes the odor molecules. It became clear.

Metal ions (capable of binding to two or more organic ligands) and organic ligands (having two or more coordination-bondable sites) are alternately linked to form a large number of three-dimensional network spaces inside. Various porous coordination polymers are known to have, and by controlling the size of the organic ligand, that is, by using a specific organic compound, it is adjusted to an arbitrary three-dimensional network space, and a specific three-dimensional network space is specified. Studies have been made on storing a large amount of gas (methane gas, carbon dioxide, etc.) (Patent Documents 3 and 4). In addition, attempts to use a gas separation filter by controlling the three-dimensional network space size of the porous coordination polymer, application of a solid electrolyte with ionic conductivity, and an attempt to use an unreacted ion site as a catalyst are being investigated. Has been done. In addition, deodorants and molded products (fibers) for daily odors (tobacco odor, animal odor, excretion odor, garbage odor, sweat odor) that utilize the gas adsorption property of this porous coordination polymer and the antibacterial property of metal ions. , Textile products, filters), antiviral agents (Patent Document 5) have been proposed. Porous coordination polymers have higher adsorption capacity and adsorption capacity than inorganic porous particles such as silica and zeolite, so when used as a deodorant, they adsorb and store more odorous substances in a shorter time. That is, effective deodorization is possible. However, depending on the type of porous coordination polymer and the design of the three-dimensional network space size, odorous substances may be released back from the porous coordination polymer and molded products due to stimuli such as heat, static electricity, and friction. There was a concern that it would replace the odorous substance of. Therefore, regardless of the type of porous coordination polymer and the design of the three-dimensional network space size, materials that stably maintain excellent deodorizing effect, antibacterial and antibacterial effect, and antiviral effect (for example, film, sheet, etc.) If tapes, plastic moldings, metal plates, tarpaulins, mesh sheets, synthetic leather, canvas, woven fabrics, fabrics, non-woven fabrics, paper, etc. are present, they can be used in various industrial fields and at home for further deodorization and antibacterial purposes. It is possible to improve the convenience in anti-woven fabric applications and further anti-virus applications.

Japanese Patent Application Laid-Open No. 2003-251728 Japanese Patent Application Laid-Open No. 2015-014093 Japanese Unexamined Patent Publication No. 2001-348361 Japanese Unexamined Patent Publication No. 2016-193957 Japanese Unexamined Patent Publication No. 2019-084499

INDUSTRIAL APPLICABILITY The present invention effectively reduces the odor concentration of all unpleasant odor components such as rot of germs, propagation of mold, biological excrement, and unpleasant odor components such as cigarette smoke, exhaust gas, and volatile chemical substances. A deodorant antibacterial antibacterial substance that stably maintains the antibacterial and antifungal properties that suppress the growth of germs and molds that can cause stinks, and also has an antibacterial effect against virus infection, and this deodorant. An object of the present invention is to provide a deodorant antibacterial antifungal coating composition containing a sex antibacterial antifungal substance and a deodorant antibacterial antifungal coating film containing the deodorant antibacterial antifungal substance. By providing this deodorant antibacterial anti-mold material, deodorant antibacterial anti-mold coating composition, and deodorant anti-bacterial anti-mold coating film, these are film, sheet, tape, plastic molded product, metal plate, tarpaulin, mesh. Used for materials such as sheets, synthetic leather, sail cloth, woven fabrics, fabrics, non-woven fabrics, paper, etc., these deodorant antibacterial anti-mold materials or materials incidental with deodorant antibacterial anti-mold coating materials are ceiling films, Space dividers, hoisting and elevating sheet shutters, curtains, wallpapers, rugs, covers, blinds, air filters, clothing, etc. are processed into factories, offices, schools, commercial facilities, hospitals, nursing homes, ceremonial halls, garbage collection sites, etc. Widely used in public toilets and zoos. In particular, the deodorant antibacterial antifungal substance of the present invention, tarpaulin, canvas or the like incidental with the deodorant antibacterial antifungal coating film can be appropriately used for a medical negative pressure tent having an air film structure.

As a result of various studies in consideration of this point, the present invention is composed of an organic complex unit and a crosslinkable organic compound, and has a porous coordination height having a three-dimensional lattice group in which both are alternately connected in multiple directions. In the molecule, by supporting a photocatalytic metal oxide in a three-dimensional lattice group, a deodorant effect that effectively reduces the odor concentration with respect to malodorous components and unpleasant odorous components in general, and germs that can cause malodors and unpleasant odors. A deodorant antibacterial and antifungal substance that stably maintains antibacterial and antifungal properties that suppress the growth of sardines and has an antibacterial effect against virus infection can be obtained. To complete the present invention, it has been found that a deodorant antibacterial anti-mold coating composition comprising the same deodorant antibacterial anti-mold coating composition can be obtained, and a deodorant anti-bacterial anti-mold coating material containing the deodorant anti-bacterial anti-mold substance can be obtained. I arrived.

That is, the deodorant antibacterial antifungal substance of the present invention is composed of an organic complex unit and a crosslinkable organic compound, and has a porous coordination polymer having a three-dimensional lattice group in which both are alternately connected in multiple directions (a porous coordination polymer (). It is a metal organic structure), and 1) the organic complex unit is composed of a compound having 1 to 6 divalent to tetravalent metal ions and 2 to 4 carboxyl groups, and 2) the crosslinkable organic compound. , An organic ligand having 2 to 4 nitrogen atoms in the structure, or an organic ligand having 1 to 2 carboxyl groups and 1 to 2 nitrogen atoms in the structure, and further said It is preferable that the group carries a photocatalytic metal oxide. A three-dimensional geometric space (a jungle gym shape not limited to a cubic lattice shape) formed by regularly connecting organic complex units in multiple directions with a crosslinkable organic compound interposed therebetween becomes a three-dimensional lattice group. .. By efficiently adsorbing malodorous components and unpleasant odorous components, this three-dimensional lattice group develops a stable and continuous deodorizing effect that reduces the odor concentration in a short time, and further has a stable and continuous antibacterial effect. It exerts an antiviral effect. In particular, since the photocatalytic metal oxide is carried in the three-dimensional lattice group, radicals generated by the photocatalytic metal oxide by photoexcitation decompose and discharge odor molecules (organic substances) by oxidative attack, and the three-dimensional lattice group over time. The inside is reset to a space where odorous substances can be captured (occluded) again. Furthermore, the radicals generated by the photocatalytic metal oxide by supporting the photocatalytic metal oxide in the three-dimensional lattice group are the cell walls / membranes of bacteria and mold, and the nucleic acids (RNA, DNA) and glycoproteins that compose the virus. Bacteria that have been damaged by the growth of bacteria, molds, and viruses by protein denaturation that breaks the bonds between the cell walls and membranes of bacteria and molds, and molecules such as nucleic acids and glycoproteins. Nucleic acid, viruses, etc. cannot propagate and lead to death. In particular, by causing changes in viral proteins, nucleic acids, etc., even if infected with a virus, the ability to bind to receptors on the surface of human cells is inactivated, thereby suppressing the infection. Since the porous coordination polymer has an organic complex unit portion, it is possible to impart antistatic properties to the article accompanying the porous coordination polymer coating film. In the crosslinkable organic compound, a space having a three-dimensional geometric shape formed by regularly connecting organic complex units in multiple directions with the crosslinkable organic compound interposed therebetween is a three-dimensional lattice group. Therefore, the larger the molecular weight of the crosslinkable organic compound, the more branches of the molecular chain, the larger the volume of the organic complex unit, or the larger the bond angle between the organic complex unit and the organic complex unit, the more the obtained three-dimensional lattice. The size of the (ie, the pores of the porous coordination polymer) becomes vast. Further, the crystal structure (shape and size of the three-dimensional lattice) having a geometric shape is arbitrarily designed by selecting 2 to 4 conformations in the chemical structure. By designing this crystal structure, it is possible to control the odorous components (chemical substances) that can be adsorbed (occluded).

In the deodorant antibacterial antifungal substance of the present invention of the present invention, the photocatalytic metal oxide is titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide. Use or use of one or more of one or more selected from the above, A) ultraviolet excitation type exhibiting activity at a wavelength of 200 nm to 399 nm, and B) visible light excitation type exhibiting activity at a wavelength of 400 nm to 780 nm. Is preferable. The ultraviolet-excited photocatalytic metal oxide of A) is suitable for outdoor use (solar excitation), and the visible light-excited photocatalytic metal oxide of B) is suitable for indoor use (fluorescent lamp, black light excitation). When the three-dimensional lattice structure of the porous coordination polymer carries these photocatalytic metal oxides, the photocatalytic activity of the photocatalytic metal oxide is expressed, and the three-dimensional lattice structure of the porous coordination polymer is contained. The captured odor gas is sequentially decomposed, and the state of the three-dimensional lattice is reset to the sky so that more odor gas can be taken in. This reset enables the permanence of repeating the cycle of adsorption / decomposition reset / adsorption. In addition, by oxidatively denaturing proteins and nucleic acids such as viruses, fungi, and molds, it is possible to suppress their growth, which also prevents putrefactive odors and mold odors. The visible light-excited photocatalytic metal oxide of B) is a co-catalyst addition (supporting) type photocatalyst, an anion-doped photocatalyst, a cation-doped photocatalyst, a co-doped photocatalyst doped with both anions and cations, and a metal halide-supported photocatalyst. Examples thereof include a type photocatalyst and an oxygen-deficient photocatalyst. In the present invention, the support of the photocatalytic metal oxide includes not only the support on the three-dimensional lattice structure but also the support in contact with the three-dimensional lattice group exposed on the surface of the porous coordination polymer.

In the deodorant antibacterial antifungal substance of the present invention of the present invention, one or more of the porous coordination polymers selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. It is preferable to carry the metal of. These metals may be in the state of ultrafine particles, atoms, or ions. Due to the coexistence of these metals, the antibacterial, antibacterial, and antiviral effects are more immediate than the oxidative attack of the photocatalytic metal oxide, and the deodorant, antibacterial, and antiviral effects of the photocatalytic metal oxide. It acts as a dope agent for enhancing the effects such as moldiness and antiviral property. Among these metals, silver (ion) and copper (ion) are particularly preferable. Supporting a metal on a porous coordination polymer is for exhibiting antibacterial, antifungal, and antiviral properties indoors and at night without UV irradiation, and is UV-excited photocatalytic metal oxidation. The purpose is to complement the function of things.

The deodorant antibacterial anti-mold coating composition of the present invention of the present invention is a deodorant antibacterial anti-mold coating composition containing a porous coordination polymer, and the porous coordination polymer is an organic complex unit. It is composed of a crosslinkable organic compound and a three-dimensional lattice group formed by alternately connecting the two in multiple directions. 1) The organic complex unit contains 1 to 6 metal ions having 2 to 4 valences and carboxyl. It consists of a compound having 2 to 4 groups, 2) and the crosslinkable organic compound is an organic ligand having 2 to 4 nitrogen atoms in the structure, or 1 to 2 carboxyl groups in the structure and It is an organic ligand having 1 to 2 nitrogen atoms, and it is preferable to carry a photocatalytic metal oxide in the three-dimensional lattice group.

In the deodorant antibacterial anti-mold coating composition of the present invention of the present invention, the photocatalytic metal oxide contains titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and oxidation. Use of one or more selected from iron, A) ultraviolet excitation type exhibiting activity at a wavelength of 200 nm to 399 nm, and B) visible light excitation type exhibiting activity at a wavelength of 400 nm to 780 nm. Alternatively, it is preferable to use them in combination.

In the deodorant antibacterial anti-mold coating composition of the present invention of the present invention, the porous coordination polymer is selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. It is preferable to carry more than a kind of metal. By supporting a metal on a porous coordination polymer, the photocatalytic metal oxide is used to develop antibacterial, antifungal, and antiviral properties in the shade where the photocatalytic metal oxide is difficult to function, and at night. It complements the function of oxides.

The deodorant antibacterial anti-mold coating composition of the present invention of the present invention preferably further contains a silanol group-containing organic silane compound or a titanol group-containing organic titanium compound. When the coating film is formed into a coating film by sol-gel condensation of these compounds, it is possible to enhance the bending strength and abrasion strength of the coating film obtained by the action of fixing the porous coordination polymer in the three-dimensional network of sol-gel condensation. can.

The deodorant antibacterial antifungal coating composition of the present invention preferably further contains a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand. As a result, the antibacterial, antifungal, and antiviral effects are more immediate than the effects of the photocatalytic metal oxide, and also affect the sustained stability of the antibacterial, antifungal, and antiviral effects. .. Further inclusion of a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand in a deodorant antibacterial antifungal coating composition is a shade in which the photocatalytic metal oxide is difficult to function. , And for the development of antibacterial, antifungal, and antiviral properties at night, complementing the function of photocatalytic metal oxides.

The deodorant antibacterial anti-mold coating film of the present invention of the present invention is a deodorant antibacterial anti-mold coating film containing a porous coordination polymer, and the porous coordination polymer is an organic complex unit and cross-linking. It is composed of a sex organic compound and has a three-dimensional lattice group formed by alternately connecting the two in multiple directions. 1) The organic complex unit contains 1 to 6 metal ions having 2 to 4 valences and a carboxyl group. It consists of 2 to 4 compounds, 2) and the crosslinkable organic compound is an organic ligand having 2 to 4 nitrogen atoms in the structure, or 1 to 2 carboxyl groups and 1 to 1 in the structure. It is an organic ligand having two nitrogen atoms, and it is preferable to further support a photocatalytic metal oxide in the three-dimensional lattice group.

In the deodorant antibacterial anti-mold coating film of the present invention, the photocatalytic metal oxide is titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide. , A) UV-excited type that exhibits activity at a wavelength of 200 nm to 399 nm, and B) visible light-excited type that exhibits activity at a wavelength of 400 nm to 780 nm. It is preferable to use it in combination.

The deodorant antibacterial anti-mold coating film of the present invention of the present invention is one in which the porous coordination polymer is selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. It is preferable to support the above metal. Supporting a metal on a porous coordination polymer is for exhibiting antibacterial, antifungal, and antiviral properties in the shade where photocatalytic metal oxides are difficult to function, and at nighttime, and is a photocatalytic metal. It complements the function of oxides.

The deodorant antibacterial anti-mold coating film of the present invention preferably contains a solgel condensate of a silanol group-containing organic silane compound or a solgel condensate of a titanol group-containing organic titanium compound as a binder component. By using these sol-gel condensates as a binder component, it is possible to fix and stabilize the porous coordination polymer in the three-dimensional network of sol-gel condensation, and enhance the bending strength and wear strength of the obtained coating film. be able to.

The deodorant antibacterial antifungal coating of the present invention of the present invention preferably further contains a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand. The inclusion of a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand in the deodorant antibacterial antifungal coating film can be used indoors without ultraviolet irradiation and even at night. It is intended to exhibit antibacterial, antifungal, and antiviral properties, and complements the functions of ultraviolet-excited photocatalytic metal oxides.

According to the above invention, the odor concentration is effectively reduced for all the malodorous components such as germ decay, breeding of mold, biological excrement, and unpleasant odorous components such as cigarette smoke, exhaust gas, and volatile chemical substances. A deodorant antibacterial and antifungal substance that stably maintains antibacterial and antifungal properties that suppress the growth of germs and molds that can cause stinks, and also has an inhibitory effect on the growth of viruses. It is possible to obtain a deodorant antibacterial antifungal coating composition containing a deodorant antibacterial antifungal substance and a deodorant antibacterial antifungal coating film containing the deodorant antibacterial antifungal substance. Deodorant property (deodorant property) can be exhibited only by the porous coordination polymer, but the photocatalytic metal oxide is supported on the three-dimensional lattice group of the porous coordination polymer layer as in the present invention. By the photocatalytic activity of the photocatalytic metal oxide, the odorous gas captured in the three-dimensional lattice group of the porous coordination polymer is sequentially decomposed and discharged, and the state of the three-dimensional lattice can be reset to empty so that more odorous gas can be taken in. can. This reset enables the permanence of repeating the cycle of adsorption / decomposition reset / adsorption. In particular, radicals generated by the photocatalytic activity of photocatalytic metal oxides attack the cell walls / membranes of bacteria and molds, and the nucleic acids (RNA, DNA) and glycoproteins that make up viruses, and the cell walls / membranes of bacteria and molds. And by protein denaturation that breaks the binding of molecules such as nucleic acids and glycoproteins, the growth of bacteria, molds, and viruses is suppressed, and the bacteria, molds, and viruses that have been damaged by the molecules can grow. By having the effect of killing without killing, it also prevents the odor of rotting and odor. In particular, by causing changes in viral proteins, nucleic acids, etc., even if infected with a virus, the ability to bind to receptors on the surface of human cells is inactivated, thereby suppressing the infection. Further, as for the photocatalytic metal oxide, the visible light excitation type photocatalyst is suitable for indoor use, and the deodorant antibacterial anti-mold coating film of the present invention has a porous coordination polymer encapsulated in a sol-gel condensate to form a coating film. Strengthen bending strength and wear strength. Therefore, according to the deodorant antibacterial anti-mold material, the deodorant antibacterial anti-mold coating composition, and the deodorant anti-bacterial anti-mold coating film of the present invention, these are film, sheet, tape, plastic molded product, metal plate, etc. Materials used for materials such as tarpaulins, mesh sheets, synthetic leather, sail cloth, textiles, fabrics, non-woven fabrics, paper, etc. Ceiling film, space partition, hoisting lift sheet shutter, curtain, wallpaper, rug, cover, blind, air filter, medical non-woven protective clothing, non-woven mask, etc. are processed into factories, offices, schools, commercial facilities, hospitals, etc. Widely used in nursing facilities, ceremonial halls, garbage collection areas, public toilets, zoos, etc. In particular, a tarpaulin containing the deodorant antibacterial antifungal substance of the present invention, a woven fabric coated with a resin such as canvas, or a tarpaulin having a deodorant antibacterial antifungal coating film on the surface, and a resin coating such as canvas. The woven fabric can be suitable for medical temporary partitions, medical negative pressure tent shelters with an inflatable temporary membrane structure.

a) The deodorant antibacterial antifungal substance of the present invention is composed of an organic complex unit and a crosslinkable organic compound, and is a porous coordination polymer having a three-dimensional lattice group formed by alternately connecting the two in multiple directions. 1) The organic complex unit consists of 1 to 6 divalent to tetravalent metal ions and 2 to 4 carboxyl groups, and 2) the crosslinkable organic compound is 2 to 4 in the structure. An organic ligand having one nitrogen atom, or an organic ligand having one or two carboxyl groups and one or two nitrogen atoms in the structure, and a photocatalytic metal oxide in a three-dimensional lattice group. The photocatalytic metal oxide to be carried is one or more selected from titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide. Either A) an ultraviolet-excited type that exhibits activity at a wavelength of 200 nm to 399 nm, or B) a visible light-excited type that exhibits activity at a wavelength of 400 nm to 780 nm, whichever is used or used in combination, and the porous coordination is required. The polymer carries one or more metals selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten.
b) The deodorant antibacterial anti-mold coating composition of the present invention is a coating composition containing the deodorant antibacterial anti-mold substance of the above a), and contains a silanol group-containing organic silane compound or a titanol group-containing organic titanium compound. A coating composition comprising a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand.
c) The deodorant antibacterial anti-mold coating film of the present invention is a coating film containing the deodorant antibacterial anti-mold coating substance of a) above, and is a solgel condensate of a silanol group-containing organic silane compound or a titanol group-containing organic titanium. It is a coating film containing a solgel condensate of a compound as a binder component, and further containing a complex of silver and an organic compound ligand, and / or a complex of copper and an organic compound ligand.

The porous coordination polymer particles are composed of an organic complex unit and a crosslinkable organic compound, and the two are alternately connected in multiple directions to form a jungle gym-like (not limited to cubic lattice-like) three-dimensional lattice group. It forms an organic structure. The porous coordination polymer particles have a crystal structure completed after an arbitrary time by mixing and stirring a solution containing an organic complex unit and a solution containing a crosslinkable organic compound (preferably high temperature × high pressure hydrothermal method). Precipitate. The reaction ratio (molar ratio) between the organic complex unit and the crosslinkable organic compound is preferably determined by computer simulation based on the metal value of the organic complex unit used and the number of crosslink points of the crosslinkable organic compound. As the solution used for the reaction, known solvents such as water, methanol, ethanol, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. The organic complex unit is a three-dimensional composite structure composed of a compound having 1 to 6 2- to 4-valent metal ions and 2 to 4 carboxyl groups, and when a crosslinkable organic compound is compared to a pillar portion, it is organic. The complex unit corresponds to the joint portion. The porosity of the porous coordination polymer corresponds to a three-dimensional lattice group in the crystal structure, and the particle size of the porous coordination polymer particles forming the porous coordination polymer is 001 μm to 10 μm. The organic complex unit has 2 to 4 valent metal ions, one metal ion in one complex part, 2 to 4 metal ion aggregates due to the same metal ion, or 5 to 6 metals due to the same metal ion. Examples include complex structures made up of ionic aggregates. Examples of the divalent metal ion include manganese ion, cobalt ion, nickel ion, copper ion, zinc ion, iron ion, magnesium ion, molybdenum ion and palladium ion. Examples of trivalent ions include chromium ions, iron ions, and aluminum ions. Examples of tetravalent ions include titanium ions and zirconium ions. In particular, it is preferable to use divalent ions (particularly cobalt ions, nickel ions, copper ions, zinc ions) or trivalent ions (particularly chromium ions, iron ions) in order to form a regular crystal structure. Although a plurality of types of metal ions constituting the porous coordination polymer may be used in combination, it is preferably used alone in order to arrange the regularity of the three-dimensional lattice group. When three or more kinds are used, the regularity of the bond may be disturbed, and it may be difficult to analyze the structure of the three-dimensional lattice of the obtained porous coordination polymer.

The compound having 2 to 4 carboxyl groups forming an organic complex unit forms a complex with the above metal ions, and is Zn ₄ O (CO _2- ⁾ ₆ , Zn ₃ O (CO _2- ⁾ ₆ , Cr ₃ O. (CO _2- ⁾ ₆ , Fe ₃ O (CO _2- ⁾ ₆ , Cu ₂ O (CO _2- ) ₄ , Zn ₂ O ₍ CO ^2- ) ₄ , Cr ₂ O _{(CO 2-) 4} ^{, Co} _{2 O} (CO _2- ⁾ ₄ , Fe ₂ O (CO _2- ⁾ ₄ , Zr ₆ O ₄ (OH) ₄ (CO _2- ) ₁₂ , Zr ₆ O ₈ (CO _2- ⁾ ₈ , Zn ₃ O ₃ (CO ₂ ⁻ ) ^- ) ₃ , Co ₃ O ₃ (CO _2- ⁾ ₃ , Ni ₃ O ₃ (CO _2- ⁾ ₃ , etc. As an aggregate of multiple metal ions having parts in the structure, 4, 6, The pillar portions are formed by forming 8 or 12 complex portions and linking them with a crosslinkable organic compound. Therefore, it is preferable to use a compound having one kind and at most two kinds of carboxyl groups in terms of molecular design and structural analysis. When three or more kinds are used, the regularity of the bond may be disturbed, and it may be difficult to analyze the structure of the three-dimensional lattice group of the obtained porous coordination polymer.

Compounds having 2 to 4 carboxyl groups forming an organic complex unit are compounds having 2 carboxyl groups in the structure, such as fumaric acid, trans, transmuconic acid, phthalic acid, isophthalic acid, terephthalic acid and biphenyl. 4,4'-Dicarboxylic acid, 2-hydroxyterephthalic acid, 9,10-anthracendicarboxylic acid, 2,5-diaminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-naphtherene terephthalic acid, 5-cyano -1,3-benzenedicarboxylic acid, 2-aminoterephthalic acid, 3,5-pyridinedicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,2'-diamino-4,4'-stilbendicarboxylic acid, 2,2 '-Dinitro-4,4'-stillbenzicarboxylic acid, etc. may be mentioned. Examples of the compound having three carboxyl groups in the structure include 1,3,5-benzenetricarboxylic acid, biphenyl-3,4', 5-tricarboxylic acid, and 1,3,5-tris (4-carboxyphenyl). Benzene, 1,3,5-tris (4'-carboxy [1,1'-biphenyl] -4-yl) benzene, 1,3,5-tris (4-carboxyphenyl) triazine, and the like can be mentioned. Examples of the compound having four carboxyl groups in the structure include biphenyl-3,3', 5,5'-tetracarboxylic acid, 3,3', 5,5'-tetracarboxydiphenylmethane, [1,1'. , 4'1 "] terphenyl-3,3", 5,5 "-tetracarboxylic acid, 1,2,4,5-tetrakis (4-carboxyphenyl) benzene, etc. These include the pillar part. Since a joint portion is formed with the crosslinkable organic compound, it is preferable to use one kind, at most two kinds of organic ligands in terms of molecular design and structural analysis. When three or more kinds are used, the binding rule. The properties may be disturbed, making it difficult to analyze the structure of the three-dimensional lattice group of the obtained porous coordination polymer. These organic complex units are regularly linked in multiple directions via a crosslinkable organic compound. The space of the three-dimensional geometric shape (jungle gym-like not limited to the cubic lattice shape) formed by this forms a three-dimensional lattice group. Therefore, the larger the molecular weight of the organic complex unit, the more branches of the molecular chain, or The larger the volume of the organic complex unit or the larger the bonding angle between the organic complex unit and the organic complex unit, the wider the size of the obtained three-dimensional lattice. The size of the three-dimensional lattice is preferably 3 nm to 12 nm. Can use a commercially available product of SIGMA-ALDRICH (Sigma Aldrich Japan GK).

The crosslinkable organic compound is arbitrary from an organic ligand having 2 to 4 nitrogen atoms in the structure, or an organic ligand having 1 to 2 carboxyl groups and 1 to 2 nitrogen atoms in the structure. Can be selected and used. Examples of the crosslinkable organic compound having two or more nitrogen atoms in the structure include pyridine and pyridine derivatives, azopyridine and azopyridine derivatives, pyrazine and pyrazine derivatives, bipyridine and bipyridine derivatives, piperidin and piperidin derivatives, dipyridyl and dipyridyl derivatives, and the like. Cyclic structure compounds having heteroatoms such as triazine and triazine derivatives, imidazole and imidazole derivatives, 1,4-diazabicyclo [2,2,2] octane, etc. at both ends can be mentioned. Examples of the crosslinkable organic compound having 1 to 2 carboxyl groups and 1 to 2 nitrogen atoms in the structure include pyridinedicarboxylic acid and pyridinedicarboxylic acid derivatives, bipyridinedicarboxylic acid and bipyridinedicarboxylic acid derivatives, and pyrazinedicarboxylic acid. And pyrazinedicarboxylic acid derivatives, pyrazoline dicarboxylic acid and pyrazoline dicarboxylic acid derivatives, pyrazole dicarboxylic acid and pyrazole dicarboxylic acid derivatives, quinoxalin dicarboxylic acid and quinoxalin dicarboxylic acid derivatives, imidazole dicarboxylic acid and imidazoline dicarboxylic acid derivatives, imidazole dicarboxylic acid and imidazole dicarboxylic acid. Acid derivative, diimide dicarboxylic acid and diimide dicarboxylic acid derivative, quinoline dicarboxylic acid and quinoline dicarboxylic acid derivative, biquinolin dicarboxylic acid and biquinolin dicarboxylic acid derivative, pyridine derivative tricarboxylic acid, bipyridine derivative tricarboxylic acid, pyrazine derivative tricarboxylic acid, pyrazoline derivative tricarboxylic Acid, pyrazole derivative tricarboxylic acid, quinoxalin derivative tricarboxylic acid, imidazoline derivative tricarboxylic acid, imidazole derivative tricarboxylic acid, diimide derivative tricarboxylic acid, quinoline derivative tricarboxylic acid, biquinolin derivative tricarboxylic acid, pyridine derivative tetracarboxylic acid, bipyridine derivative tetracarboxylic acid, pyrazine Derivative tetracarboxylic acid, pyrazoline derivative tetracarboxylic acid, pyrazole derivative tetracarboxylic acid, quinoxalin derivative tetracarboxylic acid, imidazoline derivative tetracarboxylic acid, imidazole derivative tetracarboxylic acid, diimide derivative tetracarboxylic acid, quinoline derivative tetracarboxylic acid, biquinolin derivative tetra Carboxylic acid, etc. may be mentioned. Since these form pillar portions by a crosslinkable organic compound, it is preferable to use one kind, at most two kinds of organic ligands in terms of molecular design and structural analysis. When three or more kinds are used, the regularity of the bond may be disturbed, which may make it difficult to analyze the structure of the obtained porous coordination polymer. The organic complex units are a group of three-dimensional lattices in which a space having a three-dimensional geometric shape (a jungle gym-like shape not limited to a cubic lattice shape) formed by regularly connecting organic complex units in multiple directions via these crosslinkable organic compounds. To form. Therefore, the larger the molecular weight of the crosslinkable organic compound, the more branches of the molecular chain, or the larger the volume of the crosslinkable organic compound, the wider the size of the obtained three-dimensional lattice. The size of the three-dimensional lattice is preferably 3 nm to 15 nm.

By having the organic complex unit portion, the porous coordination polymer particles impart antistatic property to the article (containing or coating film) incidental with the porous coordination polymer. The three-dimensional lattice group of the porous coordination polymer is composed of malodorous components such as germ rot, mold propagation, and biological excrement, tobacco smoke, exhaust gas, and volatile chemical substances (toluene, petroleum benzine, etc.). By adsorbing all unpleasant odor components in a short time, the odor concentration is effectively reduced, and the deodorizing effect is stable and sustained. Then, by supporting a part or all of the photocatalytic metal oxide in a part or all of the three-dimensional lattice group, the odorous gas captured in the three-dimensional lattice group (typically, ammonia odor, by the photocatalytic activity of the photocatalytic metal oxide, By sequentially decomposing and discharging mercapto odor, hydrogen sulfide odor, aging odor, indole odor, skatole odor, etc. and resetting the three-dimensional lattice to the sky, it becomes possible to take in more odorous gas. (Here, a part or all of the three-dimensional lattice group, is a part or all of the number of three-dimensional lattices, and does not mean a part or all of the volume of the three-dimensional lattice.) The photocatalytic metal oxide is titanium oxide. One or more particles having a particle diameter of 3 to 15 nm selected from titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide can be mentioned and carried in one three-dimensional lattice unit. The number of particles to be formed may be one, a plurality, or a large number, and is not particularly limited. Further, it may be supported in contact with the three-dimensional lattice group on the surface of the porous coordination polymer. In addition to the photocatalytic activity of the photocatalytic metal oxide, the odorous gas captured in the three-dimensional lattice group of the porous coordination polymer is sequentially decomposed and discharged, and the new odorous gas is captured to bring about a remarkable deodorizing effect. The radicals generated by photoexcitation of photocatalytic metal oxides attack the cell walls / membranes of bacteria and molds, and the nucleic acids (RNA, DNA) and glycoproteins that make up viruses, and the cell walls / membranes of bacteria and molds, and nucleic acids. , Suppresses the growth of bacteria, molds, and viruses by protein denaturation that breaks the binding of molecules such as glycoproteins, and the bacteria, molds, and viruses that have been damaged by the molecules cannot grow. It exerts antibacterial and antiviral effects that lead to death. In particular, by causing changes in viral proteins, nucleic acids, etc., even if infected with a virus, the ability to bind to receptors on the surface of human cells is inactivated, thereby suppressing the infection.

The photocatalytic metal oxide is one or more selected from titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide, and A) 200 nm to 399 nm. It can be used with or in combination with either an ultraviolet-excited type that exhibits activity at the wavelength of (B) or a visible light-excited type that exhibits activity at a wavelength of 400 nm to 780 nm. In particular, in the visible light excitation type of B), 1) metals such as silver, platinum, gold, copper, rhodium, palladium, ruthenium, and iridium and compounds of those metals are added to the above photocatalytic metal oxide as an auxiliary catalyst ( Anion-doped photocatalyst in which nitrogen, carbon, sulfur, phosphorus, boron, fluorine, etc. are doped into the above-mentioned photocatalytic metal oxide, 3) the above-mentioned photocatalytic metal. Cationic-doped photocatalysts in which oxides are doped with transition metal ions such as chromium, niobium, manganese, cobalt, vanadium, iron, and nickel. 4) The above photocatalytic metal oxides are doped with both anions and cations. Dope-type photocatalyst, 5) Metal halide-supporting photocatalyst in which a halide of a noble metal such as platinum, palladium, or rhodium is supported on the above-mentioned photocatalytic metal oxide, 6) Partially oxygen from the above-mentioned photocatalytic metal oxide. An example is an oxygen-deficient photocatalyst extracted from the metal. The photocatalytic metal oxide can be used alone or in combination of two or more from the above, and in particular, A) ultraviolet-excited photocatalytic metal oxide and B) visible light-excited photocatalytic metal oxidation. When used in combination with a substance, it exhibits photocatalytic activity regardless of the type of light source indoors or outdoors, and has a deodorant effect, antibacterial antifungal property, and antiviral property at all times.

In order to support the photocatalytic metal oxide on the porous coordination polymer, the porous coordination polymer is put into the above solution containing the photocatalytic metal oxide, stirred, and then isolated and dried. Therefore, the photocatalytic metal oxide particles can be supported on the surface of the porous coordination polymer and the three-dimensional lattice group. The photocatalytic metal oxide is supported on the surface of the porous coordination polymer and a part or all of the three-dimensional lattice group of the porous coordination polymer. Here, a part or all of the three-dimensional lattice group is a part or all with respect to the number of three-dimensional lattices, and does not mean a part or all with respect to the volume of the three-dimensional lattice. Further, the support of the photocatalytic metal oxide on the surface of the porous coordination polymer means the support in contact with the three-dimensional lattice group exposed on the surface of the porous coordination polymer. As for the porous coordination polymer carrying the photocatalytic metal oxide, the larger the space for taking in the odorous substance into the three-dimensional lattice group, the faster the deodorizing effect appears and the larger the capacity capacity. When the lattice is not filled with a large amount of photocatalytic metal oxide (50% or more of the volume of the three-dimensional lattice is a marginal space), the photocatalytic metal oxide is concentrated on the surface of the porous coordination polymer. The three-dimensional lattice group inside the porous coordination polymer may be preserved. The mass ratio of the porous coordination polymer to the photocatalytic metal oxide is preferably 50: 1 to 1: 1, particularly preferably 10: 1 to 3: 2.

In addition to the above photocatalytic metal oxide, the porous coordination polymer carries one or more metals selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. These metals may be in the state of ultrafine particles, atoms, or ions. Due to the coexistence of these metals, the antibacterial, antifungal, and antiviral effects are more immediate than the oxidative attack of the photocatalytic metal oxide, especially in the shade where the photocatalytic metal oxide is difficult to function and at night. It exhibits antibacterial, antifungal, and antiviral properties and complements the function of photocatalytic metal oxides. Further, it acts as a doping agent for enhancing the effects of the photocatalytic metal oxide such as deodorant property, antibacterial property, antifungal property, and antiviral property. In particular, these metal ions have the effect of reacting with the SH group of proteins involved in cell permeability of the surface layer of bacteria, molds, and viruses to inhibit the metabolism of enzymes and proteins necessary for vital activities, or the metal ions that have invaded cells. Crosses the double strand of DNA or RNA and inhibits the replication of DNA or RNA, thereby suppressing the growth of bacteria, molds, viruses and the like. In particular, by causing changes in viral proteins, nucleic acids, etc., even if infected with a virus, the ability to bind to receptors on the surface of human cells is inactivated, thereby suppressing the infection. Among these metals, silver, silver ion, copper and copper ion are particularly preferable. In order to support these metals and metal ions on the porous coordination polymer, the porous coordination polymer was put into a solution containing the above-mentioned photocatalytic metal oxide and these metals and metal ions and stirred. After that, by isolation and drying, the photocatalytic metal oxide particles, the metal, and the metal ion can be supported on the surface of the porous coordination polymer and the three-dimensional lattice group. These metal ions include chlorides, bromides, iodides, oxides, hydroxides, sulfates, glass oxides, carbonic acids, organic acids (acetic acid, lactic acid, oxalic acid, phosphoric acid, thiosian acid, etc.), etc. The source is the metal salt of.

The deodorant antibacterial antifungal coating composition of the present invention is a coating composition containing the deodorant antibacterial antifungal substance described in paragraphs [0023] to [0030], and the general-purpose binder component of this coating material is a thermoplastic resin. Known resins such as heat-curable resin and ultraviolet-curable resin can be used in solvent-soluble type or emulsion type, but when a coating film is formed, the resin is porous, which is a deodorant antibacterial and antifungal substance. There is a concern that the coordinating polymer will be buried and block the three-dimensional lattice group of the porous coordinating polymer, which will significantly reduce the ability to adsorb odorous gas. Therefore, it is preferable that the deodorant antibacterial antifungal coating composition of the present invention contains a silanol group-containing organic silane compound or a titanol group-containing organic titanium compound. The deodorant antibacterial antifungal coating film of the present invention is formed by a sol-gel condensation reaction by applying and drying (heat treating) this coating composition. When this coating composition is formed into a thin film coating film by sol-gel condensation of these compounds, the three-dimensional lattice group of the porous coordination polymer is formed by the action of fixing the porous coordination polymer particles in the three-dimensional network of sol-gel condensation. It can be controlled so as not to be extremely blocked. The charging ratio of the silanol group-containing organic silane compound or the titanol group-containing organic titanium compound contained in the deodorant antibacterial anti-mold coating composition is the blending amount of the porous coordination polymer (supporting a photocatalytic metal oxide or the like). On the other hand, 1: 4 to 2: 1, particularly preferably 1: 2 to 3: 2. Further, the charging ratio of the silanol group-containing organic silane compound or the titanol group-containing organic titanium compound contained in the deodorant antibacterial anti-mold coating composition is a porous coordination polymer (supporting a photocatalytic metal oxide and described later). 1: 4 to 2: 1, particularly preferably 1: 2 to 3: 2, with respect to the blending amount of (the hydrolyzate of the alkoxysilane compound of the above). The solvent contained in the deodorant antibacterial anti-mold coating composition is mainly a water / alcohol solvent, and the concentration of the silanol group-containing organic silane compound or the titanol group-containing organic titanium compound (or the concentration of these hydrolysates) is 0. 1 to 30% by mass, particularly preferably 1 to 10% by mass. The hydrolysis accelerator of the silanol group-containing organic silane compound for forming the solgel condensate, or the titanol group-containing organic titanium compound is a metal alkoxide in which an alkoxy group is bonded to metals such as aluminum, titanium, and zirconium, or these. Metal chelate compounds that can form keto-enol mutants in metal alkoxides, inorganic acids (hydrochloride, nitrate, phosphoric acid, etc.), organic acids (girate, acetic acid, benzenesulfonic acid, etc.), ammonia, organic amines, dibutyltin Using dilaurate, dibutyltin dioctite, etc. as a hydrolysis catalyst, use about 0.01 to 1% by mass based on the mass of the silanol group-containing organic silane compound or the titanol group-containing organic titanium compound, and use 3 at room temperature to 60 ° C. Stir for ~ 24 hours. The deodorant antibacterial antifungal coating film of the present invention is formed by a sol-gel condensation reaction by applying and drying (heat treating) this coating composition.

Further, by binding the hydrolyzate of the alkoxysilane compound to the porous coordination polymer, the adhesion between the porous coordination polymer and the sol-gel condensate is improved, and at the same time, the bending strength and the abrasion strength of the coating film are improved. To increase. The alkoxysilane compound is a compound having two or more different reactive groups in the molecule represented by the general formula: XR-Si (Y) ₃ , for example, X = amino group, vinyl group, epoxy group, methacrylic group, and the like. Acrylic group, chlor group, mercapto group, isocyanurate group, isocyanate group, etc. (R = alkyl chain), Y = methoxy group, ethoxy group and the like. Examples of the silane coupling agent include aminosilane, vinylsilane, epoxysilane, methacrylicsilane, acrylicsilane, chlorsilane, mercaptosilane, isocyanuratesilane, and isocyanatesilane. The treatment for binding the hydrolyzate of the alkoxysilane compound to the porous coordination polymer may be performed by using the porous coordination polymer (either before or after supporting the photocatalytic metal oxide particles). Treat in an aqueous solution containing one or more alkoxysilane compounds at a concentration of 1-5% by mass, and hydrolyze the alkoxysilane compound: XR-Si (OH) ₃ (X, Y are the same as above) in a porous manner. This is a process of binding to an unreacted carboxy group of a coordination polymer, a metal ion, or the like. Further, the porous coordination polymer to which the hydrolyzate of the alkoxysilane compound is bonded is used together with a component capable of forming a solgel condensate such as an organosilicate compound, a silanol group-containing organic silane compound, and a titanol group-containing organic titanium compound. However, it is preferable that the porous coordinating polymer is densely packed in the solgel condensate. The porous coordination polymer to which the hydrolyzate of the alkoxysilane compound is bonded becomes a coating film that is somehow incorporated into a part of the bonds in the sol-gel condensate, and has adhesion strength with the substrate and surface wear strength. To improve. The deodorant antibacterial anti-mold coating film of the present invention is formed by coating a coating composition containing a porous coordination polymer to which a hydrolyzate of this alkoxysilane compound is bonded, and a solgel condensation reaction by drying (heat treatment). ..

The silanol group-containing organic silane compound is a tetrafunctional hydrolyzable silane compound represented by the chemical formula: SiO (OR) ₄ , in which R is an alkyl group having 1 to 10 carbon atoms (particularly 1 to 3 carbon atoms). (Lower alkyl group), or aryl group (particularly phenyl group), specifically tetramethoxysilane (Si (OCH ₃ ) ₄ : also known as tetramethylsilicate), tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ : alias. Tetraethyl silicate), tetrapropoxysilane (Si (OC ₃ H ₇ ) ₄ : also known as tetrapropyl silicate), tetrabutoxysilane (Si (OC ₄ H ₉ ) ₄ : also known as tetrabutyl silicate), tetraphenoxysilane (Si (OC ₆ )). H ₆ ) ₄ : Also known as tetraphenyl silicate), dimethoxydiethoxysilane (Si (OCH ₃ ) ₂ (OC ₂ H ₅ ) ₂ : also known as dimethyl diethyl silicate), and the like. The multimer of the silanol group-containing organic silane compound is a condensate represented by the chemical formula: Syn On _-1 (OR) 2 ( _{n + 1)} , in which R is an alkyl group having 1 to 10 carbon atoms (1 to 10 carbon atoms). In particular, a lower alkyl group having 1 to 3 carbon atoms), an aryl group (particularly a phenyl group), or n is a degree of mulnation (so-called n-mer) representing the number of condensed molecules of a tetrafunctional hydrolyzable silane compound, and n is 2. The above silanol group-containing organic silane compound multimer is a multimer formed by condensing two or more molecules by the reaction between silanol groups produced by hydrolysis of a tetrafunctional hydrolyzable silane compound, and is represented by n. The degree of quantification means the number of Si atoms contained in one molecule of the multimer. In the present invention, it is preferable that the sol-gel condensate layer is made of a silanol group-containing organic silane compound multimer (Si _{nOn -1} (OR) _{2 (n + 1)} ) having a degree of mass increase of 2 to 10, preferably 4 to 6. .. If the atomic arrangement of this solgel condensate layer is modeled on a square lattice network consisting of horizontal and vertical axes, Si atoms are arranged at the intersections of the horizontal and vertical axes, and between Si-Si atoms adjacent to each other on the top, bottom, left, and right. It is an image in which O atoms are arranged.

The titanium group-containing organic titanium compound is a tetrafunctional hydrolyzable titanium compound represented by the chemical formula: TiO (OR) ₄ , in which R is an alkyl group having 1 to 10 carbon atoms (particularly 1 to 3 carbon atoms). (Lower alkyl group), or aryl group (particularly phenyl group), specifically tetramethoxytitanium (Ti (OCH ₃ ) ₄ : also known as tetramethyltitanate), tetraethoxytitanium (Ti (OC ₂ H ₅ ) ₄ : alias. Tetraethyl Titanium), Tetrapropoxytitanium (Ti (OC ₃ H ₇ ) ₄ : Also known as Tetrapropyl Titanate), Tetrabutoxy Titanium (Ti (OC ₄ H ₉ ) ₄ : Also known as Tetrabutyl Titanium), Tetraphenoxy Titanium (Ti (OC ₆ ) H ₆ ) ₄ : Titanium alkoxide compounds such as (also known as tetraphenyl titanate), dimethoxydiethoxytitanium (Ti (OCH ₃ ) ₂ (OC ₂ H ₅ ) ₂ : also known as dimethyldiethyl titanate), as well as tributoxytitanium stearate, iso. Titanium acylate compounds such as propoxytitanium tristearate: Ti (OOCR) _n , and further titanium chelate compounds such as diisopropoxytitanium bisacetylacetonato and diisopropoxytitanium bisethylacetoacetate: (ROO) ₂ Ti (OR) ₂ . Examples of the complex and others include isopropoxytitanium triisostearate, isopropoxytitanium dimethacrylate isostearate, isopropoxytitanium trisdioctyl phosphate, bisdioctyl phosphate ethylene glycolate titanium, and dibutoxybistriethanol aminatotitanium. The multimer of the titanol group-containing organic titanium compound is a condensed product represented by the chemical formula: Tin On _-1 (OR) 2 ( _{n + 1)} , in which R is an alkyl group having 1 to 10 carbon atoms (particularly). A lower alkyl group having 1 to 3 carbon atoms), an aryl group (particularly a phenyl group), or n is a degree of mulchification (so-called n-mer) representing the number of condensed molecules of a tetrafunctional hydrolyzable titanium compound, and n is 2 or more. The titanol group-containing organic titanium compound multimer is a multimer produced by condensing two or more molecules by the reaction between titanol groups produced by hydrolysis of a tetrafunctional hydrolyzable titanium compound, and is represented by n. Degree means the number of Ti atoms contained in one molecule of the multimer. In the present invention, a sol-gel condensate layer made of a _titanol group-containing organic titanium compound multimer (Tin On _-1 (OR) _{2 (n + 1)} ) having a degree of mass increase of 2 to 10, preferably 4 to 6, is preferable. If the atomic arrangement of this solgel condensate layer is modeled on a square lattice network consisting of horizontal and vertical axes, Ti atoms are arranged at the intersections of the horizontal and vertical axes, and between Ti-Ti atoms adjacent to each other on the top, bottom, left, and right. It is an image in which O atoms are arranged.

The deodorant antibacterial antifungal coating composition of the present invention may further contain a complex of silver and an organic compound ligand, and / or a complex of copper and an organic compound ligand. As a result, the antibacterial, antibacterial, and antiviral effects are more immediate than the effects of the photocatalytic metal oxide, and the antibacterial and antibacterial properties at night and in the shade where the photocatalytic metal oxide is difficult to function. , And exhibits antiviral properties and complements the function of photocatalytic metal oxides. In particular, these metal complexes have the effect of inhibiting the metabolism of enzymes and proteins necessary for vital activities by reacting with the SH groups of proteins involved in cell permeability of the surface layers of bacteria, molds, and viruses, or the metals that have invaded cells. Ions cross the double strand of DNA or RNA and inhibit the replication of DNA or RNA, thereby suppressing the growth of bacteria, molds, viruses and the like. In particular, by causing changes in viral proteins, nucleic acids, etc., even if infected with a virus, the ability to bind to receptors on the surface of human cells is inactivated, thereby suppressing the infection. Preferred examples of the organic compound ligand include amino acids, ethylenediamine, triethylenetetramine, bipyridine, ethyleneamineacetic acid, pyrithione, phenanthroline, porphyrin, crown ether and the like, and silver ions include silver bromide, silver chloride, and the like. Sources are silver salts such as silver citrate, silver iodide, silver lactate, silver nitrate, silver oxide, silver picrinate, and copper is disodium copper citrate, triethanolamine copper, copper carbonate, cupric ammonium carbonate, It is obtained from copper salts such as cupric hydroxide, copper chloride, cupric chloride, ethylenediamine copper complex, copper oxychloride, copper sulfate oxychloride, cuprous oxide and copper thiosianate as a source. The deodorant antibacterial anti-mold coating film of the present invention is coated and dried (heat-treated) of a coating composition containing the complex of silver and an organic compound ligand and / or the complex of copper and an organic compound ligand. Formed by.

Specific examples of the organic compound ligand include amino acids such as glycine, histidine, and methionine, ethylenediamine, triethylenetetramine, bipyridine, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, and 1,3-propanediaminetetraacetic acid. Ethylenediamineacetic acid such as acetic acid, diethyltriaminepentaacetic acid, triethylenetetraminehexacetic acid, pyrithione, phenanthroline, porphyrin, and cyclic polyether compounds. Cyclic polyether compounds are 9-crown-3,12-crown-4,15-crown-5,18-crown-6,21-crown-7,24-crown-8,27-crown-9,30- Crown-10,33-Crown-11, 36-Crown-12, Dibenzo12-Crown-4, Dibenzo18-Crown-6, Tribenzo18-Crown-6, Dibenzo24-Crown-8, Tribenzo27-Crown-9 , Dibenzo 30-crown-10, dibenzo 36-crown-12, tribenzo 36-crown-12, tetrabenzo 36-crown-12 (these are abbreviated representations of the ether ring of crown ether, and the first number is the total number of atoms. The number at the end represents the number of oxygen atoms), which is a coordination by incorporating metal ions into the ring structure. Further, the three-dimensional structures of these plurality of crown ethers, cryptand [2.2] and cryptand [2.2.2], and some or all of the oxygen atoms of these crown ethers are replaced with nitrogen atoms (NH). Aza crown ethers, and thiaza crown ethers in which some or all of the oxygen atoms of these crown ethers are replaced with sulfur atoms (SH), and crown ethers such as derivatives thereof can be mentioned for one metal ion. This includes those in which a plurality of ligands are coordinated, and those in which a single metal ion is sandwiched and shared by a ring structure of a plurality of crown ethers. Specific examples thereof include histidine / silver, glycine / copper, pyrithione / copper, triethylenetetramine / copper, dibenzo24-crown-8 / copper, and dibenzo24-crown-8 / silver. The complex of silver and the organic compound ligand and / or the complex of copper and the organic compound ligand is based on the blending amount of the porous coordination polymer particles (supporting a photocatalytic metal oxide or the like). 20: 1 to 2: 1, particularly preferably 10: 1 to 3: 1.

The deodorant antibacterial anti-mold coating composition of the present invention is used for materials such as films, sheets, tapes, plastic molded products, metal plates, tarpaulins, mesh sheets, synthetic leathers, sail cloths, woven fabrics, fabrics, non-woven fabrics, and papers. These materials, which are accompanied by deodorant antibacterial antifungal coatings, are ceiling films, space dividers, hoisting lift sheet shutters, curtains, wallpaper, rugs, covers, blinds, air filters, medical non-woven protective clothing, etc. It is processed into non-woven fabric masks, etc., and is widely used in factories, offices, schools, commercial facilities, hospitals, nursing homes, ceremonial halls, garbage collection areas, public toilets, zoos, etc. In particular, a tarpaulin containing the deodorant antibacterial antifungal substance of the present invention, a woven fabric coated with a resin such as canvas, or a tarpaulin having a deodorant antibacterial antifungal coating film on the surface, and a resin coating such as canvas. The woven fabric can be suitable for medical temporary partitions, medical negative pressure tent shelters with an inflatable temporary membrane structure. The tarpaulin is a laminate (0.3 mm to 1.5 mm thick) in which a woven fabric is sandwiched between two or more resin films (0.1 mm to 0.5 mm thick) on the front side and the back side, and the canvas is a woven fabric. Both sides were coated with resin (deping), impregnated and coated, and then dried and solidified to form a composite of resin and woven fabric (thickness of 0.35 mm to 1 mm), and a resin film on the front side was heat-fused onto this composite. It is a laminated body (thickness of 0.5 mm to 1.5 mm). The woven fabric is a woven fabric consisting of a warp and a weft, a triaxial woven fabric consisting of a warp and an upper left bias yarn / upper right bias yarn, a warp, a weft, and a quadruaxial woven fabric consisting of an upper left bias yarn / upper right bias yarn. As the woven fabric consisting of warp and weft, woven fabrics such as plain woven fabric, diagonal woven fabric, twill woven fabric, red woven fabric, and mojiri woven fabric ⁽ gauze woven fabric, woven fabric) can be used. A suitable rate is 0 to 25%. As these woven fabrics, those that have undergone known dyeing arrangement processing such as scouring, bleaching, dyeing, softening, water repellency, mold proofing, flame proofing, and calendar can also be used. The threads that make up the fabric are synthetic fibers, natural fibers (cotton, kenaf, etc.), semi-synthetic fibers (rayon), inorganic fibers (glass, silica, alumina, carbon fibers, etc.) and mixed fibers consisting of two or more of these. Any fiber can be used, but for general purposes, polypropylene fiber, polyethylene fiber, polyvinyl alcohol fiber, polyester (polyethylene terephthalate: PET, polybutylene terephthalate: PBT, polynaphthalene terephthalate: PNT, etc.) fiber, nylon fiber, etc. One or more kinds selected from 1) multifilament yarn, 2) short fiber spun yarn, 3) and covering yarn made of aramid fiber and synthetic fiber such as blended fiber (blended / combined twist). Threads can be used. These multifilament yarns include bulky processed yarns such as Taslan yarns and Woolly yarns.

The thermoplastic resin of the thermoplastic resin composition used for resin coating processing such as tarpaulin and sail cloth is a soft vinyl chloride resin (containing a plasticizer), a vinyl chloride-based copolymer resin, a chlorinated vinyl chloride resin, and an olefin resin (PE, PP), olefin-based copolymer resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene- (meth) acrylic acid (ester) copolymer resin, urethane resin, vinyl acetate-based copolymer resin, styrene-based It is a thermoplastic resin or elastomer having a shore A hardness of about 35 to 85, such as a copolymer resin, a polyester-based copolymer resin, and a fluorine-containing copolymer resin, and these include urethane rubber, acrylic rubber, butadiene rubber, and chlor. It may contain sulfonated polyethylene, SBR, EPDM, EPM and the like to enhance rubber elasticity. Elastomer is a block copolymer resin composed of two or more kinds of monomers, and each block component constitutes a hard segment and a soft segment. Among these thermoplastic resins and elastomers, soft vinyl chloride resin having high frequency welding property, vinyl chloride-based copolymer resin, chlorinated vinyl chloride resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene- ( Meta) Acrylic acid (ester) copolymer resin, urethane resin, fluorine-containing copolymer resin and the like are preferable. The thermoplastic resin composition is mainly composed of the above-mentioned thermoplastic resin, and is mainly a stabilizer, a filler, a colorant, a pigment, a metallic pigment, a phosphorescent pigment, a flame retardant, a flame retardant, an ultraviolet absorber, a light stabilizer, and an organic fungicide. Known additives such as agents, deodorants, antistatic agents, and cross-linking agents can be arbitrarily combined and blended.

The present invention will be further described with reference to the following examples and comparative examples, but the embodiments of the present invention are not limited to the scope of these examples. In Examples and Comparative Examples, the deodorant property, antibacterial property, antifungal property, and antiviral property of the test sheet were measured and evaluated by the following test methods.
<Deodorant>
Four Tedlar® gas barrier bags with a volume of 5 L were prepared, and each bag was adjusted to a concentration of 10 ppm. Four types of chemical gas, 1) ammonia (basic), 2) isovaleric acid (acidic), 3 sets of 4 bags each containing 3 L of hydrogen sulfide (acidic) and 4) toluene (VOC) were prepared.
Put a 10 cm × 10 cm size test sheet (formation of a coating film containing a porous coordination polymer on one side) in the bag in the order of 1) → 2) → 3) → 4), and black light (peak 365 nm). Under the environment of irradiation or fluorescent light irradiation (irradiation to the surface on which the coating film containing the porous coordination polymer is formed: irradiation distance 2.5 cm: sealed in a tedler bag), 25 ° C x 30 minutes and 25 ° C x 60 minutes, respectively. , 25 ° C. × 120 minutes, each gas concentration after being allowed to stand indoors was measured with a gas detector tube (Gastech).
* Black light model SL-B01A5 (Ohm Electric Co., Ltd.) Examples 1-5, 7-10
W55mm x H160mm x D25mm
* Straight tube fluorescent lamp 4W (FL4D) x 2 (Panasonic Corporation) Examples 6 and 10
In addition, the result of a comparison test of the deodorizing effect with and without black light or fluorescent lamp without irradiating the sheet-shaped test piece of the example with black light or fluorescent lamp was treated as a reference example.
<Antibacterial>
Antibacterial (JIS Z2801: 2010 compliant)
Sheet-shaped test piece (Example, comparative example) is inoculated by dropping the bacterial solution on the surface (inoculation number ¹⁰⁴ ), and the bacterial solution and the test piece sheet-like material so that the test piece is in contact with the bacterial solution. Incubate for 24 hours under the conditions of black light (peak 365 nm) irradiation (irradiation to the surface of the coating film containing porous coordination polymer: irradiation distance 2.5 cm) in an environment of 35 ° C. and a relative humidity of 90% or more. did. After culturing, the test piece sheet was washed away, the viable cell count per 1 cm ² was measured, and the antibacterial activity value (the bacterial count log value in the test piece sheet form of the Example or Comparative Example was subtracted from the bacterial count logarithmic value in the target group). Value) was calculated.
In addition, the result of a comparison test of the antibacterial effect with and without black light or fluorescent lamp without irradiating the sheet-shaped test piece of the example with black light or fluorescent lamp was treated as a reference example.
The numerical value in the table is the number of viable bacteria per 1 cm ² of the test piece, and "ND" is defined as "Not Detected". A 1/200 NB medium was used as the bacterial solution adjusting solution. The bacterial species used are shown below.
Staphylococcus aureus subsp. Aures 12732 "Staphylococcus aureus subsp.
Escherichia coli NBRC 3972
* Black light model SL-B01A5 (Ohm Electric Co., Ltd.) Examples 1-5, 7-10
W55mm x H160mm x D25mm
* Straight tube fluorescent lamp 4W (FL4D) x 2 (Panasonic Corporation) Examples 6 and 10
<Moldproof: JIS Z 2911 culture test>
A sheet-like material (example, comparative example) having a width of 3 cm and a length of 3 cm is inoculated with the following test mold spores, placed on a potato / dextrose agar medium, and irradiated with black light (peak 365 nm) or fluorescent light. Under the condition (irradiation of the surface on which the coating film containing the porous coordination polymer was formed: irradiation distance 2.5 cm), the state of mold generation was observed at 28 ° C. for 7 days and 14 days, and evaluated according to the following criteria.
In addition, the result of a comparison test of the antifungal effect with and without black light or fluorescent lamp without irradiating the sheet-shaped test piece of the example with black light or fluorescent lamp was treated as a reference example.
1: No hyphal growth is observed in the inoculated area 2: The area of the hyphal growth area observed in the inoculated area does not exceed 1/3 of the total area 3: The area of the hyphal growth area observed in the inoculated area is the entire area <Test mold> (A) + (B) + (C) mixed mold that exceeds 1/3 of the area (A) Aspergillus niger NBRC 105649 (black mold)
(B) Penicillium citrinum NBRC 6352 (Penicillium)
(C) Cladosporium cladosporioides NBRC 6348 (Kurokawa mold)
* Black light model SL-B01A5 (Ohm Electric Co., Ltd.) Examples 1-5, 7-10
W55mm x H160mm x D25mm
* Straight tube fluorescent lamp 4W (FL4D) x 2 (Panasonic Corporation) Examples 6 and 10
<Antiviral (ISO 21720)>
* Antibacterial test method for plastic products: ISO 22196 (JIS Z2801) compliant Test method: Kaken Test Center Method 5 cm x 5 cm test piece (formation of coating film containing porous coordination polymer, containing porous coordination polymer) 0.4 ml of cat calicivirus (a low-risk pathogen among the pathogens stipulated in the Infectious Diseases Control Law) solution is dropped onto the (coating not formed), covered with a 4 cm x 4 cm film, and allowed to stand at 25 ° C. x 24 hours (. Black light: After irradiation with a peak of 365 nm or irradiation with a fluorescent lamp (irradiation to the surface of the coating film containing the porous coordination polymer: irradiation distance of 2.5 cm), the antiviral activity value is measured.
The anti-virus activity value is 24 hours for the anti-virus processed product from the average value of the common logarithm of the virus infection titer (PFU / cm ² ) after leaving the test piece without a coating film containing a porous coordination polymer for 24 hours. Antivirus activity value 2.0 or more (virus reduction rate 1/100 or more, antivirus activity value 3.0), which is the value obtained by subtracting the average value of the common logarithm of the virus infection titer (PFU / cm ² ) after standing. The above is judged to be effective with the virus reduction rate 1/1000).
In addition, the results of a comparison test of the antiviral effect depending on the presence or absence of black light or fluorescent lamp without irradiating the sheet-shaped test piece of the example with black light or fluorescent lamp are treated as reference examples. did.

[Example 1]
< Woven fabric >
PET multifilament threads made of 1000 denier (1111 dtex) polyethylene teletalate (PET) fibers (192 filaments) and subjected to S twist 50 T / m are used for the warp and weft groups, and the warp groups are 1 inch apart. A plain woven fabric having a woven structure of 16 threads and a group of wefts having a woven structure of 16 threads per inch was used. The mass of this woven fabric was 150 g / m ² , and the porosity (total gap) was 14%.
< Sheet base material >
Using this woven fabric as a base material, a 0.2 mm thick calendar molded film made of the following [Formulation 1] soft vinyl chloride resin composition is used as a coating layer on the front and back surfaces, and melt laminating is performed by thermocompression bonding with a laminator. A sheet substrate having a thickness of 0.7 mm and a mass of 830 g / m ² was obtained.
[Formulation 1]: Soft vinyl chloride resin composition (compound)
Vinyl chloride resin (K value 71.5) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl) (plasticizer)
55 parts by mass Tricredil phosphate (flame retardant plasticizer) 10 parts by mass Evaporated soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimon trioxide (flame retardant) 10 parts by mass Rutyl type Titanium oxide (white pigment) 5 parts by mass Bentriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass
< Porosity Coordination Polymer (1) >
Metal-organic framework particles (synthetic product by hydrothermal method) having a particle diameter of 0.5 to 1 μm formed by a multiaxial alternating linkage with the following organic complex unit and a crosslinkable organic compound were used.
Organic complex unit: Copper terephthalate "Cu ₂ (C ₆ H ₄ CO ₂ ) ₄ "
Crosslinkable organic compound: 1,4-diazabicyclo [2,2,2] octane "C ₆ H ₁₂ N ₂ "
<Support of photocatalytic metal oxides and metal ions>
Porous coordination polymer (1), photocatalytic titanium oxide sol (primary particle diameter 5 nm: ultraviolet excitation type showing activity at wavelengths from 200 nm to 399 nm), silver nitrate, water (50% by mass) / ethanol (50% by mass) In this order, the solution containing 20 (solid content): 10 (solid content): 0.5 (solid content): 100 was stirred in a closed container at 80 ° C. for 2 hours, and then the filtrate was dried. Then, a porous coordination polymer (1a) carrying a photocatalytic metal oxide and silver ions on the surface and inside was obtained.
< Treatment with alkoxysilane compound >
Porous coordination polymer (1a), alkoxysilane compound (epoxysilane: 3-glycidoxypropyltrimethoxysilane), and water in this order at a mass ratio of 10 (solid content): 1 (solid content): 100. The blended solution was stirred in a closed container at 30 ° C. for 2 hours, and then the filtrate was dried to obtain a porous coordination polymer (1b) to which a hydrolyzate of an eposisilane compound was bound.
< Composition for forming a coating film containing a porous coordination polymer >
The composition (1) for forming a coating film containing a porous coordination polymer according to the following [Formulation 2] was blended.
Next, the composition (1) for forming a coating film containing a porous coordination polymer was gravically coated on one surface of the sheet substrate with a gravure roll of 100 meshille, and heated and dried in a hot air furnace at 120 ° C. for 2 minutes. Then, the solgel curing of the composition for forming the porous coordination polymer-containing coating film (1) is completed and converted into the porous coordination polymer-containing coating film (1) to obtain a deodorant antibacterial anti-mold coating film. An accompanying sheet-like material (1) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained.
[Formulation 2] Composition for forming a coating film containing a porous coordination polymer (1))
Ethyl silicate (Si (OC ₂ H ₅ ) ₄ : SiO ₂ equivalent 40% by mass) 5% by mass, and
A mixture of 95% by mass of the tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ].
25 parts by mass Hydrolysis catalyst: 2% hydrochloric acid 1 part by mass Porous coordination polymer (1b) 10 parts by mass 18-monoazathia crown ether-5 / silver (cyclic polyether metal complex) 1 part by mass *-(CH) ₂ CH ₂ S) ₅ CH ₂ CH ₂ NH- is made into a ring, and silver ions are carried in the ring.
Water (50% by mass) / Ethanol (50% by mass) 100 parts by mass

[Example 2]
The same as in Example 1 except that the composition in which the porous coordination polymer (1) of Example 1 was changed to the porous coordination polymer (2) was used, and a deodorant antibacterial anti-mold coating film was attached. A sheet-like product (2) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained.
< Porosity Coordination Polymer (2) >
Metal-organic framework particles (synthetic product by hydrothermal method) having a particle diameter of 0.5 to 1 μm formed by a multiaxial alternating linkage with the following organic complex unit and a crosslinkable organic compound were used.
Organic complex unit: Zinc terephthalate "Zn ₄ O (C ₆ H ₄ CO ₂ ) ₆ "
Crosslinkable organic compound: 1,4-diazabicyclo [2,2,2] octane "C ₆ H ₁₂ N ₂ "
<Support of photocatalytic metal oxides and metal ions>
Using the porous coordination polymer (2), the same procedure as in the production process of the porous coordination polymer (1a) of Example 1 is carried out, and the photocatalytic metal oxide and the silver ion are carried on the surface and inside. A sex coordination polymer (2a) was obtained.
< Treatment with alkoxysilane compound >
Using the porous coordination polymer (2a), the same procedure as the production process of the porous coordination polymer (1b) of Example 1 was carried out, and the porous coordination polymer to which the hydrolyzate of the epoxysilane compound was bonded (the porous coordination polymer (1b). 2b) was obtained.

[Example 3]
The same as in Example 1 except that the composition in which the porous coordination polymer (1) of Example 1 was changed to the porous coordination polymer (3) was used, and a deodorant antibacterial anti-mold coating film was attached. A sheet-like product (3) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained.
< Porosity Coordination Polymer (3) >
Metal-organic framework particles (synthetic product by hydrothermal method) having a particle diameter of 0.5 to 1 μm formed by a multiaxial alternating linkage with the following organic complex unit and a crosslinkable organic compound were used.
Organic complex unit: Copper 2,6-naphthalenedicarboxylate "Cu ₂ (C ₁₀ H ₆ CO ₂ ) ₄ "
Crosslinkable Organic Compounds: 1,4-diazabicyclo [2,2,2] Octane "C ₆ H ₁₂ N ₂ "
<Support of photocatalytic metal oxides and metal ions>
Using the porous coordination polymer (3), the same procedure as in the production process of the porous coordination polymer (1a) of Example 1 is carried out, and the photocatalytic metal oxide and the silver ion are carried on the surface and inside. A sex coordination polymer (3a) was obtained.
< Treatment with an alkoxysilane compound >
Using the porous coordination polymer (3a), the same procedure as the production process of the porous coordination polymer (1b) of Example 1 was carried out, and the porous coordination polymer to which the hydrolyzate of the epoxysilane compound was bonded (the porous coordination polymer (1b). 3b) was obtained.

[Example 4]
The same as in Example 1 except that the composition in which the porous coordination polymer (1) of Example 1 was changed to the porous coordination polymer (4) was used, and a deodorant antibacterial anti-mold coating film was attached. A sheet-like product (4) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained.
< Porosity Coordination Polymer (4) >
Metal-organic framework particles (synthetic product by hydrothermal method) having a particle diameter of 0.5 to 1 μm formed by a multiaxial alternating linkage with the following organic complex unit and a crosslinkable organic compound were used.
Organic complex unit: Copper 2,3-pyrazinedicarboxylate "Cu ₂ (C ₄ H ₂ N ₂ CO ₂ ) ₄ "
Crosslinkable organic compound: Pyridine "C ₅ H ₅ N"
<Support of photocatalytic metal oxide particles and metal ions>
Using the porous coordination polymer (4), the same procedure as in the production process of the porous coordination polymer (1a) of Example 1 is carried out, and the photocatalytic metal oxide and the silver ion are carried on the surface and inside. A sex coordination polymer (4a) was obtained.
< Treatment with alkoxysilane compound >
Using the porous coordination polymer (4a), the same procedure as the production process of the porous coordination polymer (1b) of Example 1 was carried out, and the porous coordination polymer to which the hydrolyzate of the epoxysilane compound was bonded (the porous coordination polymer (1b). 4b) was obtained.

[Example 5]
The same as in Example 1 except that the composition in which the porous coordination polymer (1) of Example 1 was changed to the porous coordination polymer (5) was used, and a deodorant antibacterial anti-mold coating film was attached. A sheet-like product (5) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained.
< Porosity Coordination Polymer (5) >
Metal-organic framework particles (synthetic product by hydrothermal method) having a particle diameter of 0.5 to 1 μm formed by a multiaxial alternating linkage with the following organic complex unit and a crosslinkable organic compound were used.
Organic complex unit: Copper 1,3,5-benzenetricarboxylate "Cu ₃ (C ₆ H ₄ CO ₂ ) ₆ "
Crosslinkable organic compound: Pyridine "C ₅ H ₅ N"
<Support of photocatalytic metal oxides and metal ions>
Using the porous coordination polymer (5), the same procedure as the production process of the porous coordination polymer (1a) of Example 1 was carried out, and the porous coordination height was carried out to support the photocatalytic metal oxide on the surface and inside. The molecule (5a) was obtained.
< Treatment with alkoxysilane compound >
Using the porous coordination polymer (5a), the same procedure as the production process of the porous coordination polymer (1b) of Example 1 was carried out, and the porous coordination polymer to which the hydrolyzate of the epoxysilane compound was bonded (the porous coordination polymer (1b). 5b) was obtained.

[Example 6]
A photocatalytic titanium oxide sol (primary particle diameter 5 nm: an ultraviolet-excited type exhibiting activity at a wavelength of 200 nm to 399 nm) supported on the porous coordination polymer (1) of Example 1 is subjected to a photocatalytic tungsten oxide sol / Cu. / Pt ion co-supporting (primary particle diameter 5 nm: visible light excited type showing activity at a wavelength of 400 nm to 780 nm) is replaced with a porous coordination polymer (1), which is porous in the same manner as in Example 1. A sex coordination polymer (6a) was obtained. This (6a) is a porous coordination polymer (6b) to which a hydrolyzate of an eposisilane compound is bonded, and a sheet having a thickness of 0.7 mm and a mass of 833 g / m ² is attached with a coating film containing (6b). A compound (6) was obtained.

[Example 7]
The porous coordination polymer (7a) is the same as in Example 1 except that the silver ion carried on the porous coordination polymer (1) of Example 1 is replaced with copper ion (copper ion source is copper sulfate). ) Was obtained. This (7a) is a porous coordination polymer (7b) to which a hydrolyzate of an eposisilane compound is bonded, and a sheet having a thickness of 0.7 mm and a mass of 833 g / m ² is attached with a coating film containing (7b). A compound (7) was obtained.

[Example 8]
[Formulation 2] 1 part by mass of 18-monoazathia crown ether-5 / silver (cyclic polyether metal complex) used in the composition (1) for forming a coating film containing a porous coordination polymer of Example 1 was added. A coating film containing a porous coordination polymer (1b) is attached in the same manner as in Example 1 except that the 18-diaza crown ether-4 / copper (cyclic polyether metal complex) is changed to 1 part by mass. A sheet-like product (8) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained.
* 18-Diaza crown ether-4 / copper carries copper ions in a ring of-[(CH ₂ CH ₂ NH (CH ₂ CH ₂ O) ₂ ] _2- .

[Example 9]
Ethyl silicate (Si (OC ₂ H ₅ ) ₄ : SiO ₂ equivalent 40% by mass) used in [Formulation 2] composition for forming a coating film containing a porous coordination polymer (1) of Example 1, 5% by mass, And 25 parts by mass of the mixture of 95% by mass of the tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ], ethyl titanate (Ti (OC ₂ H ₅ ) ₄ : 40 mass in terms of TIO ₂ ). %) 5% by mass, and [Ti ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ] tetraethoxytitanium pentamer was replaced with 25 parts by mass of the mixture of 95% by mass, as in Example 1. A sheet-like material (9) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained, which was accompanied by a coating film containing the porous coordination polymer (1b).

[Example 10]
50% by mass of the photocatalytic titanium oxide sol (primary particle diameter 5 nm: ultraviolet excitation type exhibiting activity at a wavelength of 200 nm to 399 nm) carried on the porous coordination polymer (1) of Example 1 is 400 nm to 780 nm. The porous coordination polymer (8b) was used in the same manner as in Example 1 except that it was replaced with 50% by mass of a visible light responsive titanium oxide sol (Si / N co-doped: Fe ion co-catalyst) showing activity at the wavelength of. A sheet-like product (10) having a thickness of 0.7 mm and a mass of 833 g / m ² was obtained, which was accompanied by the contained coating film. Only in Example 10, a black light and a straight fluorescent lamp were irradiated in combination.

The sheet-like materials (1) to (5) of Examples 1 to 5 are sheet-like materials in which a deodorant antibacterial anti-mold coating film is provided on the surface of the sheet base material, and the porous coordination height contained in the coating film is high. A sol-gel condensation including a process of supporting a photocatalytic metal oxide on a porous coordination polymer and a porous coordination polymer carrying a photocatalytic metal oxide in an embodiment in which the molecule carries a photocatalytic metal oxide. It involves the process of forming a coating. Although the tendency of odor reduction for each type of gas of ammonia, isovaleric acid, hydrogen sulfide, and toluene is different, the gas concentration increases as the time elapses, such as black light irradiation conditions, test time of 30 minutes, 60 minutes, and 120 minutes. It decreased significantly, and after 120 minutes, almost all of them were less than 1 ppm. It was also excellent in antibacterial, antifungal, and antiviral effects under black light irradiation conditions. As reference examples 1 to 5, when the sheet-like objects (1) to (5) of Examples 1 to 5 were not irradiated with black light, deodorant / deodorant effect, antibacterial property, antifungal property, and antiviral property. The sexual effect was slightly inferior. However, regardless of the activity or inactivity of the photocatalytic metal oxide, the presence of the porous coordination polymer layer alone has sufficient deodorizing / deodorizing effects, antibacterial properties, antibacterial properties, and antiviral effects. It was expressed. The reason for this is that the porous coordination polymer itself has deodorizing and deodorizing ability, that the porous coordination polymer carries silver ions, and that the complex of the metal and the organic compound ligand is used. By the combined use of 18-monoazathia crown ether-5 / silver, the composition is essentially provided with a high degree of antibacterial, anti-mold, and anti-viral properties. Therefore, a coating film formed from a composition containing the deodorant antibacterial antibacterial substance of the present invention by using a porous coordination polymer carrying a photocatalytic metal oxide in this structure and irradiating it with ultraviolet rays. The sheet-like substance having a film was further excellent in deodorizing / deodorizing effect, antibacterial property, anti-ultraviolet property, and anti-virus property. In addition, carrying silver ions on a porous coordination polymer and using 18-monoazathia crown ether-5 / silver as a complex between a metal and an organic compound ligand is a photocatalytic metal oxide. It exhibits antibacterial, antifungal, and antiviral properties in the shade, which is difficult to function, and at night, and complements the functions of photocatalytic metal oxides.

Further, since the sheet-like substances (6) to (10) of Examples 6 to 10 are the arrangements of the embodiment of Example 1 and the porous coordination polymer (1) is common, the numerical values in these various evaluation items are used. The results were similar to those of Example 1 and comparable to those of Example 1. Example 6 is an embodiment in which the photocatalytic metal oxide to be carried on the porous coordination polymer (1) is changed from an ultraviolet-excited type (titanium oxide) to a visible light-excited type (tungsten oxide: co-supported with Cu / Pt ions). Example 7 is an embodiment in which the metal ion carried on the porous coordination polymer (1) is changed from silver ion to copper ion, and Example 8 is an 18-monoazathia crown used in combination with the porous coordination polymer (1). In the embodiment in which ether-5 / silver is changed to 18-diazacrown ether-4 / copper, in Example 9, the coating film containing the porous coordination polymer (1) is a solgel condensate of a silanol group-containing organic silane compound. In Example 10, the photocatalytic metal oxide to be carried on the porous coordination polymer (1) is an ultraviolet-excited type (titanium oxide) and a visible light-excited type (titanium oxide). Tungsten oxide: Cu / Pt ion co-supporting) is used in combination.

[Comparative Examples 1 to 5]
From the porous coordination polymers (1 to 5) of Examples 1 to 5, the support of the photocatalytic metal oxide by the titanium oxide sol is omitted, and the porous coordination polymer (1') that does not support the photocatalytic metal oxide is omitted. Sheet-shaped products (11 to 15) were obtained as the same manufacturing process as in Examples 1 to 5 except that they were used in (5'). The obtained sheet-like material (11 to 15) has a deodorizing effect and antibacterial effect as compared with the sheet-like material (1 to 5) of Examples 1 to 5 by omitting the support of the photocatalytic metal oxide. Although it was inferior in properties, antifungal properties, and antiviral properties, the adsorption effect of the three-dimensional lattice group of the porous coordination polymer (1 to 5) was exhibited, and the porous coordination polymer (1 to 5) was exhibited. Due to the effect of silver ions carried on 5) and the effect of 18-monoazathia crown ether-5 / silver used in combination with the porous coordination polymer (1-5), appropriate antibacterial properties and appropriate antifungal properties It developed sex and antiviral properties at the level near the passing line.

[Comparative Examples 6 to 10]
Examples 1 to 5 except that the support of silver ions on the porous coordination polymers (1 to 5) of Comparative Examples 1 to 5 was omitted, and the combined use of 18-monoazathia crown ether-5 / silver was omitted. A sheet-like product (16 to 20) was obtained as the same manufacturing process as in 5. The obtained sheet-like substances (16 to 20) have an adsorption effect by the three-dimensional lattice group of the porous coordination polymer (1 to 5) as compared with the sheet-like substances (1 to 5) of Examples 1 to 5. However, since it does not support silver ions on the porous coordination polymer (1-5) and there is no combined use of 18-monoazathia crown ether-5 / silver, it has sufficient antibacterial properties. No anti-polymer and anti-viral properties were expressed.

[Reference Examples 1 to 5]
Reference Examples 1 to 5 are the same as Examples 1 to 5, but since the irradiation with black light is omitted, the porous coordination polymer (1 to 5) carries the photocatalytic metal oxide, but is photocatalytic. The test was performed with the metal oxide remaining inactive. By omitting the black light irradiation, it was inferior in deodorant effect, antibacterial property, antibacterial property, and antiviral property, but it was adsorbed by the three-dimensional lattice group of the porous coordination polymer (1 to 5). The deodorant property due to the effect was exhibited. In addition, due to the effect of silver ions carried on the porous coordination polymer (1-5) and the effect of 18-monoazathia crown ether-5 / silver used in combination with the porous coordination polymer (1-5). , Appropriate antibacterial property, moderate anti-polymer property, and anti-viral property at the level near the passing line. Therefore, by supporting the photocatalytic metal oxide on the porous coordination polymer (1 to 5) and further irradiating it with black light, the deodorant effect, the antibacterial property, the antibacterial effect, and the antiviral effect. It is clear that it will further improve.

INDUSTRIAL APPLICABILITY According to the present invention, deodorant that effectively reduces the odor concentration against all malodorous components such as germ decay, breeding of mold, biological excrement, and unpleasant odorous components such as cigarette smoke, exhaust gas, and volatile chemical substances. A deodorant antibacterial antifungal substance that stably maintains antibacterial and antifungal properties that suppress the growth of germs and molds that can cause stinks, and also has an inhibitory effect on the growth of viruses. It is possible to obtain a deodorant antibacterial anti-mold coating composition containing a deodorant antibacterial anti-mold substance and a deodorant anti-bacterial anti-mold coating film containing the deodorant anti-bacterial anti-mold substance. Deodorant property (deodorant property) can be exhibited only by the porous coordination polymer, but the photocatalytic metal oxide is supported on the three-dimensional lattice group of the porous coordination polymer layer as in the present invention. By the photocatalytic activity of the photocatalytic metal oxide, the odorous gas captured in the three-dimensional lattice group of the porous coordination polymer is sequentially decomposed and discharged, and the state of the three-dimensional lattice can be reset to empty so that more odorous gas can be taken in. can. This reset enables the permanence of repeating the cycle of adsorption / decomposition reset / adsorption. In particular, radicals generated by the photocatalytic activity of photocatalytic metal oxides attack the cell walls / membranes of bacteria and molds, and the nucleic acids (RNA, DNA) and glycoproteins that make up viruses, and the cell walls / membranes of bacteria and molds. And by protein denaturation that breaks the binding of molecules such as nucleic acids and glycoproteins, the growth of bacteria, molds, and viruses is suppressed, and the bacteria, molds, and viruses that have been damaged by the molecules can grow. By having the effect of killing without killing, it also prevents the odor of rotting and odor. In particular, by causing changes in viral proteins, nucleic acids, etc., even if infected with a virus, the ability to bind to receptors on the surface of human cells is inactivated, thereby suppressing the infection. Further, as for the photocatalytic metal oxide, the visible light excitation type photocatalyst is suitable for indoor use, and the deodorant antibacterial anti-mold coating film of the present invention has a porous coordination polymer encapsulated in a sol-gel condensate to form a coating film. Strengthen bending strength and wear strength. Therefore, according to the deodorant antibacterial anti-mold material, the deodorant antibacterial anti-mold coating composition, and the deodorant anti-bacterial anti-mold coating film of the present invention, these are film, sheet, tape, plastic molded product, metal plate, etc. It is used for materials such as tarpaulin, mesh sheet, synthetic leather, sail cloth, textile, cloth, non-woven fabric, paper, etc. Ceiling film, space partition, hoisting lift sheet shutter, curtain, wallpaper, rug, cover, blind, air filter, medical non-woven protective clothing, non-woven mask, etc. are processed into factories, offices, schools, commercial facilities, hospitals, etc. Widely used in nursing facilities, ceremonial halls, garbage collection areas, public toilets, zoos, etc. In particular, a tarpaulin containing the deodorant antibacterial antifungal substance of the present invention, a woven fabric coated with a resin such as canvas, or a tarpaulin having a deodorant antibacterial antifungal coating film on the surface, and a resin coating such as canvas. The woven fabric can be suitable for medical temporary partitions, medical negative pressure tent shelters with an inflatable temporary membrane structure.

Claims (13)

It is a porous coordination polymer composed of an organic complex unit and a crosslinkable organic compound and having a three-dimensional lattice group in which both are alternately connected in multiple directions. 1) The organic complex unit is 2 to 4 It consists of a compound having 1 to 6 valent metal ions and 2 to 4 carboxyl groups, and 2) the crosslinkable organic compound is an organic ligand having 2 to 4 nitrogen atoms in its structure, or It is an organic ligand having 1 to 2 carboxyl groups and 1 to 2 nitrogen atoms in its structure, and is characterized by carrying a photocatalytic metal oxide in the three-dimensional lattice group. Sexual antibacterial and antifungal substance. The photocatalytic metal oxide is one or more selected from titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide, and A) from 200 nm. The deodorant antibacterial anti-mold substance according to claim 1, wherein either an ultraviolet-excited type exhibiting activity at a wavelength of 399 nm or a visible light-excited type exhibiting activity at a wavelength of 400 nm to 780 nm is used or used in combination. .. The invention according to claim 1 or 2, wherein the porous coordination polymer carries one or more metals selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. Deodorant antibacterial anti-cobalt substance. A deodorant antibacterial anti-mold coating composition containing a porous coordination polymer, wherein the porous coordination polymer is composed of an organic complex unit and a crosslinkable organic compound, both of which alternate in multiple directions. The organic complex unit is composed of 1 to 6 2- to 4-valent metal ions and 2 to 4 carboxyl groups, and 2) the cross-linking property. The organic compound is an organic ligand having 2 to 4 nitrogen atoms in the structure, or an organic ligand having 1 to 2 carboxyl groups and 1 to 2 nitrogen atoms in the structure, and further. A deodorant antibacterial anti-mold coating composition characterized by supporting a photocatalytic metal oxide in the three-dimensional lattice group. The photocatalytic metal oxide is one or more selected from titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide, and A) from 200 nm. The deodorant antibacterial anti-mold coating material according to claim 4, wherein either an ultraviolet-excited type exhibiting activity at a wavelength of 399 nm or a visible light-excited type exhibiting activity at a wavelength of 400 nm to 780 nm is used or used in combination. Composition. The fourth or fifth aspect of claim 4 or 5, wherein the porous coordination polymer carries one or more metals selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. Deodorant antibacterial anti-cobalt coating composition. The deodorant antibacterial anti-mold coating composition according to any one of claims 4 to 6, further comprising a silanol group-containing organic silane compound or a titanol group-containing organic titanium compound. The deodorant antibacterial anti-mold coating composition according to any one of claims 4 to 7, further comprising a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand. A deodorant antibacterial anti-mold coating film containing a porous coordination polymer, wherein the porous coordination polymer is composed of an organic complex unit and a crosslinkable organic compound, both of which alternate in multiple directions. It has a group of three-dimensional lattices that are linked, and 1) the organic complex unit is composed of 1 to 6 divalent to tetravalent metal ions and 2 to 4 carboxyl groups, and 2) the crosslinkable organic. The compound is an organic ligand having 2 to 4 nitrogen atoms in the structure, or an organic ligand having 1 to 2 carboxyl groups and 1 to 2 nitrogen atoms in the structure, and further described above. A deodorant antibacterial anti-mold coating material characterized by supporting a photocatalytic metal oxide in a three-dimensional lattice group. The photocatalytic metal oxide is one or more selected from titanium oxide, titanium peroxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide, and A) from 200 nm. The deodorant antibacterial anti-mold coating according to claim 9, wherein either the ultraviolet-excited type exhibiting activity at a wavelength of 399 nm or the visible light-excited type exhibiting activity at a wavelength of 400 nm to 780 nm is used or used in combination. film. The 9 or 10 according to claim 9 or 10, wherein the porous coordination polymer carries one or more metals selected from silver, copper, zinc, cobalt, aluminum, nickel, palladium, molybdenum, and tungsten. Deodorant antibacterial anti-cobalt coating. The deodorant antibacterial antifungal coating film according to any one of claims 9 to 11, wherein the sol-gel condensate of a silanol group-containing organic silane compound or the sol-gel condensate of a titanol group-containing organic titanium compound is used as a binder component. The deodorant antibacterial antifungal coating film according to any one of claims 9 to 12, further comprising a complex of silver and an organic compound ligand and / or a complex of copper and an organic compound ligand.