WO2019087856A1 - Odor inhibition method, composition, wiper, and spray - Google Patents

Abstract

The present invention provides an odor inhibition method with which it is possible to inhibit the odor of an object to be deodorized. The present invention also provides a composition, a wiper, and a spray. This odor inhibition method inhibits odor originating with bacteria by contacting a composition containing at least one selected from the group consisting of an inorganic substance containing a first metal, an inorganic substance containing a second metal which is different from the first metal, and an organic substance containing the second metal with an object to be deodorized which contains at least one bacterium selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella genera.

Description

Method for suppressing odor, composition, wiper and spray

The present invention relates to an odor control method, a composition, a wiper and a spray.

Compositions containing silver and having antibacterial properties are known. For example, Patent Document 1 describes a “spray composition containing a silver component containing at least one selected from the group consisting of silver ions and silver colloid particles, and an adhesion agent”.

Unexamined-Japanese-Patent No. 2006-282629

The present inventors attempted to suppress odor by applying the composition described in Patent Document 1 to deodorants having various odors. However, it has been found that the odor can not be sufficiently suppressed even if the above composition is used depending on the deodorant. Then, this invention makes it a subject to provide the odor suppression method which can suppress the odor of a deodorant. Another object of the present invention is to provide a composition, a wiper and a spray.

MEANS TO SOLVE THE PROBLEM The present inventors found out that the said subject is solved by the following structures, as a result of earnestly examining in order to solve the said subject.

[1] At least one selected from the group consisting of an inorganic substance containing a first metal, an inorganic substance containing a second metal different from the first metal, and an organic substance containing a second metal And a deodorant comprising at least one type of bacteria selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella, and a composition comprising And an odor control method for suppressing odor derived from bacteria by bringing them into contact with each other.
[2] A metal-supported inorganic support, wherein the first metal-containing inorganic substance comprises a first metal single substance, a first metal oxide, and an inorganic support and a first metal supported on the inorganic support The odor suppression method as described in [1] which is at least 1 sort (s) selected from the group which consists of.
[3] A metal-supported inorganic support, wherein the second metal-containing inorganic substance comprises a second metal single substance, a second metal oxide, and an inorganic support and a second metal supported on the inorganic support The odor suppression method as described in [1] or [2] which is at least 1 sort (s) selected from the group which consists of.
[4] The composition according to any one of [1] to [3], wherein the composition contains an inorganic substance containing a second metal, the first metal is silver, and the second metal is copper. Odor control method.
[5] The odor control method according to any one of [1] to [4], wherein the composition further contains at least one selected from the group consisting of water and alcohol.
[6] The composition comprises a second metal-containing inorganic substance, and the first metal-containing inorganic substance comprises a metal-supported metal having a first inorganic carrier and silver supported on the first inorganic carrier. Any of [1] to [5], which is an inorganic support, and the second metal-containing inorganic substance is a metal-supported inorganic support having a second inorganic support and copper supported on the second inorganic support. The odor control method described in crab.
[7] The odor according to any one of [1] to [6], wherein the composition further comprises an inorganic substance containing a first metal and a third metal different from any of the second metals. How to control.
[8] The odor suppression method according to [7], wherein the inorganic substance containing the third metal contains a phosphorus atom.
[9] The odor suppression method according to any one of [1] to [8], wherein the pH of the composition is 6.5 or less.
[10] The odor control method according to any one of [1] to [9], wherein the composition further comprises a hydrophilic binder precursor, and a hydrophilic component selected from the group consisting of hydrophilic binders. .
[11] The odor suppression method according to [10], wherein the hydrophilic component contains at least one selected from the group consisting of a silicate compound, a monomer having a hydrophilic group, and a polymer having a hydrophilic group.
[12] The odor control method according to any one of [1] to [11], wherein the composition further contains at least one member selected from the group consisting of nonionic dispersants and anionic dispersants.
[13] A wiper having a base cloth and a composition impregnated in the base cloth is used to wipe off the deodorant to bring the composition into contact with the deodorant, [1] to [12] The odor control method as described in any of the above.
[14] By using a spray having a spray container and the composition contained in the spray container, the composition is sprayed onto the deodorant by using the spray container to bring the deodorant into contact with the composition, [1] The odor control method according to any one of [12].
[15] At least one selected from the group consisting of an inorganic substance containing a first metal, an inorganic substance containing a second metal different from the first metal, and an organic substance containing a second metal And a deodorant comprising at least one type of bacteria selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella, and a membrane comprising And an odor suppressing method for suppressing odor derived from bacteria by bringing them into contact with each other.
[16] A metal-supported inorganic support, wherein the first metal-containing inorganic substance comprises a first metal single substance, a first metal oxide, and an inorganic support and a first metal supported on the inorganic support The odor suppression method as described in [15] which is at least 1 sort (s) selected from the group which consists of.
[17] A metal-supported inorganic support, wherein the second metal-containing inorganic substance comprises a second metal single substance, a second metal oxide, and an inorganic support and a second metal supported on the inorganic support. [15] or [16], which is at least one selected from the group consisting of
[18] The odor according to any one of [15] to [17], wherein the film contains an inorganic substance containing a second metal, the first metal is silver, and the second metal is copper. How to control.
[19] The film according to the present invention contains a second metal-containing inorganic substance, and the first metal-containing inorganic substance is a metal-supported inorganic substance having a first inorganic support and silver supported on the first inorganic support. The carrier according to any one of [15] to [18], which is a metal-supported inorganic support comprising a second metal-containing inorganic substance having a second inorganic support and copper supported on the second inorganic support. The odor control method as described in.
[20] The odor suppression according to any one of [15] to [19], wherein the film further contains an inorganic substance containing a third metal different from any of the first metal and the second metal. Method.
[21] The odor suppression method according to [20], wherein the inorganic substance containing the third metal further contains a phosphorus atom.
[22] The odor suppression method according to any one of [15] to [21], wherein the pH of the membrane surface of the membrane is 6.5 or less.
[23] The odor control method according to any one of [15] to [22], wherein the film further comprises a hydrophilic binder.
[24] The odor suppression method according to any one of [15] to [23], wherein the film further contains at least one selected from the group consisting of nonionic dispersants and anionic dispersants.
[25] At least one selected from the group consisting of an inorganic substance containing a first metal, an inorganic substance containing a second metal different from the first metal, and an organic substance containing a second metal And used for suppressing an odor derived from at least one type of bacteria selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella. Composition.
[26] A metal-supported inorganic support, wherein the first metal-containing inorganic substance comprises a first metal single substance, a first metal oxide, and an inorganic support and a first metal supported on the inorganic support. The composition according to [25], which is at least one selected from the group consisting of
[27] A metal-supported inorganic support, wherein the second metal-containing inorganic substance comprises a second metal single substance, a second metal oxide, and an inorganic support and a second metal supported on the inorganic support. The composition according to [25] or [26], which is at least one selected from the group consisting of
[28] The composition according to any one of [25] to [27], which contains an inorganic substance containing a second metal, the first metal is silver, and the second metal is copper.
[29] The composition according to any one of [25] to [28], wherein the composition further comprises at least one selected from the group consisting of water and an alcohol.
[30] The inorganic substance containing a second metal-containing inorganic substance, the first metal-containing inorganic substance is a metal-supported inorganic support having a first inorganic support and silver supported on the first inorganic support. The inorganic substance containing a second metal is a metal-supported inorganic support having a second inorganic support and copper supported on the second inorganic support, according to any one of [25] to [29]. Composition.
[31] The composition according to any one of [25] to [30], wherein the composition further comprises an inorganic substance containing a first metal and a third metal different from any of the second metals. object.
[32] The composition according to [31], wherein the third metal-containing inorganic substance further contains a phosphorus atom.
[33] The composition according to any one of [25] to [32], which has a pH of 6.5 or less.
[34] The composition according to any one of [25] to [33], further comprising a hydrophilic binder precursor and a hydrophilic component selected from the group consisting of a hydrophilic binder.
[35] The composition according to any one of [25] to [34], wherein the film further contains at least one member selected from the group consisting of nonionic dispersants and anionic dispersants.
[36] A spray comprising a spray container and the composition according to any one of [25] to [35] housed in the spray container.
[37] A wiper comprising a base cloth and the composition according to any one of [25] to [35] impregnated in the base cloth.

According to the present invention, it is possible to provide an odor suppression method capable of suppressing the odor of a deodorant. The present invention can also provide a composition, a wiper and a spray.

Hereinafter, the present invention will be described in detail.
The description of the configuration requirements described below may be made based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of groups (atom groups) in the present specification, those not showing substitution or non-substitution have a substituent together with one having no substituent, as long as the effects of the present invention are not impaired. Is also included. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The same is true for each compound.
Moreover, in the present specification, “(meth) acrylate” represents both or either of acrylate and / or methacrylate, “(meth) acrylic” represents both or either of acrylic and methacryl, “(meth) acrylate” ) Acryloyl represents either or both of acryloyl and methacryloyl.
Further, in the present specification, a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.

[First embodiment of odor control method]
An odor control method according to a first embodiment of the present invention includes an inorganic substance containing a first metal, an inorganic substance containing a second metal different from the first metal, and a second metal. Composition comprising at least one selected from the group consisting of organic substances, Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, and Pseudomonas. A deodorant containing at least one type of bacteria (hereinafter also referred to as "specific bacteria") selected from the group consisting of Serratia sp. And Morganella sp. It is the odor suppression method which suppresses the odor originating in the said specific bacteria.

The present inventors applied the composition described in Patent Document 1 to various deodorants, and tried to suppress the odor. With the deodorants containing specific bacteria, the odor was sufficient. It was found that it was not suppressed. Although this reason is not necessarily clear, when the said deodorant contains the said specific bacteria, it originates in the said specific bacteria (for example, by the metabolism of the said specific bacteria), an odor generate | occur | produces, and this odor is fully suppressed. It was guessed that it was not done.
As a result of earnestly examining the method of suppressing the odor derived from the specific bacteria based on the above-mentioned findings, the present inventors have achieved the present invention.

Although it does not restrict | limit especially as a method to contact a composition to a deodorizer, For example, the following method is mentioned.
· Method of wiping a deodorant using a wiper having a base cloth and a composition impregnated in the base cloth and bringing the composition into contact with the deodorant (wipe method)
Method of spraying a composition onto a deodorant using a spray having a spray container and a composition accommodated in the spray container to bring the deodorant into contact with the composition (spray method)

(Wipe method)
In the wipe method, a wiper impregnated with a composition to be described later is used. It does not restrict | limit especially as a method to wipe off a deodorant (the detail of a deodorant is mentioned later) using a wiper, A well-known method can be used.

The base fabric used in the present method is not particularly limited, and may be formed of natural fibers or may be formed of chemical fibers.
Natural fibers include, for example, pulp, cotton, hemp, flax, wool, camel, cashmere, mohya, silk and the like.
Materials for chemical fibers include rayon, polynozic, acetate, triacetate, nylon, polyester, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyalkylene para oxybenzoate, and polychlore, etc. .

Among these base fabrics, hydrophilic base fabrics are preferable in that the composition is easily impregnated. The hydrophilic base is, for example, a base containing a fiber having a hydrophilic group such as a hydroxyl group, an amino group, a carboxy group, an amido group, and a sulfonyl group. Specific examples of the hydrophilic base cloth include vegetable fibers, cotton, pulp, animal fibers, rayon, nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.
Among them, as the base fabric, non-woven fabric, cloth, towel, gauze, cotton wool and the like are mentioned, and among them, non-woven fabric is preferable.
The basis weight (mass per unit area) of the base fabric is preferably 100 g / m ² or less. The amount of impregnation at the time of impregnating the composition with the base fabric is preferably an amount of one or more times the mass of the base fabric.

(Spray method)
The spray method uses a spray having a spray container and a composition contained in the spray container. It does not restrict | limit especially as a method to spray a composition to a deodorant using a spray, A well-known method can be used.
Typically, the spray includes a trigger form, a pump form, and an aerosol form in which the spray container is filled with the composition and the propellant. The propellant is not particularly limited, and examples thereof include liquefied petroleum gas and the like.

[Deodorant]
The said deodorant contains specific bacteria. There is no particular limitation on the form of the deodorant containing the specific bacteria.
The deodorant preferably further contains a substrate. The substrate is not particularly limited, and includes lecithin, methionine, urea, choline and the like. That is, the deodorant preferably contains a specific bacterium and a substrate.
There is no particular limitation on the form in which the deodorant contains the specific bacteria and the substrate. The substrate is typically urine (meaning urine of human and non-human animals, in particular urine of human and non-human animals afflicted with urinary tract infections is preferred), feces, sweat, sputum and The present invention is more effective when it is often contained in food waste, etc., and the substrate is contained in urine or feces, and is particularly excellent when the substrate is contained in urine. Exert an effect.
The form of the deodorant will be specifically described taking the case where the substrate is contained in urine as an example.
As the deodorant, one in which urine containing specific bacteria is absorbed or adsorbed in the substrate, one in which urine containing specific bacteria is disposed on the substrate, urine itself containing specific bacteria, etc. Can be mentioned. In this case, the substrate is not particularly limited, and examples thereof include clothes including underwear, care products such as bedding and diapers, toilet bowls, floors, walls and the like.

In the deodorant, it is presumed that an offensive odor substance (odor) is produced from a specific bacterium. For example, in the deodorant containing urine, urea (substrate) in the urine is decomposed by urease typically expressed by a specific bacterium to generate ammonia. As described above, it is speculated that the odorous substance (odor) is generated from the above-mentioned deodorant due to the specific bacteria.

More specifically, the present method comprises: It has an excellent effect by suppression of the odor derived from the above-mentioned bacteria in deodorant.

〔Composition〕
The composition contains a first metal-containing inorganic substance (hereinafter also referred to as “inorganic substance (1)” or “first metal-containing substance”), and a second metal different from the first metal. At least one selected from the group consisting of an inorganic substance (hereinafter also referred to as "inorganic substance (2)") and the organic substance containing the second metal (hereinafter also referred to as "second metal-containing substance") is contains.
In addition, in this specification, when only calling it a "metal", a metal simple substance (metal simple particle), a metal ion, and the metal atom contained in a compound shall be included.

<Inorganic substance (1)>
The composition contains an inorganic substance (1). The content of the inorganic substance (1) in the composition is not particularly limited, but generally, 0.001 to 80% by mass is preferable with respect to the total solid content of the composition. As the inorganic substance (1), one type may be used alone, or two or more types may be used in combination. When using 2 or more types of inorganic substances (1) together, it is preferable that total content is in the said range.

The inorganic substance (1) may be a solid substance or a liquid substance, but the inorganic substance (1) is preferably a solid substance from the viewpoint of being excellent by the effect of the present invention, and the solid substance is a particle (composition Among them, those present as particles) are more preferred.

The inorganic substance (1) contains a first metal. The form of the inorganic substance (1) is not particularly limited, and may be any of the first metal single particle (metal single particle), the first metal ion, and the first metal-containing inorganic compound. And mixtures thereof. In addition, the inorganic substance (1) may be a complex of an inorganic compound and a first metal. The complex includes, for example, an inorganic carrier, and a first metal (first metal single particle (metal single particle) supported on the inorganic carrier, an ion of the first metal, and a first metal. Metal supported carrier (hereinafter also referred to as "first metal supported inorganic carrier").
Among them, the inorganic substance (1) is a simple substance (particle) of a first metal, an ion of a first metal, an oxide of a first metal, and a first metal-supporting inorganic substance from the viewpoint of being excellent by the effects of the present invention. At least one selected from the group consisting of carriers is preferable, and the first metal-supported inorganic carrier is more preferable.

The first metal is not particularly limited, and silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel and the like can be mentioned, among which silver, copper, or Zinc is preferred, silver or copper is more preferred, and silver is even more preferred.
The inorganic substance (1) may be, for example, an oxide, a nitride, a halide, a cyanide, a selenide, a sulfide, a telluride, a salt of the first metal, etc. of the first metal. As the first metal salt, for example, arsenate, hydrogen fluoride salt, bromate, chlorate, chromate, cyanate, hexafluoroantimonate, hexafluoroarsenate, hexafluoro Phosphate, iodate, isothiocyanate, molybdate, nitrate, nitrite, perchlorate, permanganate, perrhenate, phosphate, selenate, selenite, sulfuric acid And salts, sulfites, tetrafluoroborates, tetratungstates, thiocyanates, vanadates and the like.

The inorganic support of the first metal-supported inorganic support is not particularly limited, but inorganic oxides (for example, zeolite: crystalline aluminosilicate), silica gels, and silicates such as clay minerals; glass (including water-soluble glass Zirconium phosphate; calcium phosphate; activated carbon; and the like.
In the present specification, the inorganic support of the first metal-supported inorganic support may be referred to as the "first inorganic support".

More specifically, as inorganic carriers, zinc calcium phosphate, calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicate, activated carbon, activated alumina, silica gel, glass (silicon oxide), zeolite, apatite, hydroxyapatite, phosphorus And titanium oxide, potassium titanate, hydrous bismuth oxide, hydrous zirconium oxide, and hydrotalcite.
The inorganic carrier may be crystalline or non-crystalline (amorphous), but is preferably non-crystalline. In other words, glass is preferable as the inorganic carrier.
As a material which can comprise glass, a silicate, borosilicate, and phosphate etc. (In other words, silicate glass, borosilicate glass, and phosphate glass etc.) are mentioned. Among them, silicates are preferred.
It is preferable that the said silicate contains 1 or more types of atoms chosen from the group which consists of an alkali metal and alkaline-earth metal, and aluminum silicate is more preferable.

As the first metal-supported inorganic support, metal-supported zeolite, metal-supported apatite, metal-supported glass, metal-supported zirconium phosphate, or metal-supported calcium silicate, on which the first metal is supported, is preferable, and metal-supported apatite, Or metal support glass is more preferable, and metal support glass is still more preferable.

When the inorganic substance (1) is a particle, the average particle size of the particles of the inorganic substance (1) is not particularly limited, but generally 0.01 μm or more is preferable, 0.05 μm or more is more preferable, and 20 μm or less is preferable, 15 micrometers or less are more preferable.
In addition, the average particle diameter of the particle | grains of inorganic substance (1) can be measured by observing using an electron microscope. Specifically, for the particles of the inorganic substance (1), the above-mentioned average particle diameter is a primary particle and a secondary particle (Note that “secondary particle” is an aggregate formed by fusion or contact of primary particles with each other) 90% of the total number of particles excluding the 5% of the number of particles on the small diameter side and the 5% of the particles on the large diameter side of the total particle number. The average particle diameter in the range of That is, the average particle size is a value determined from primary particles and secondary particles. Moreover, a diameter means the circumscribed circle equivalent diameter of particle | grains.
In addition, when there is no big difference in the particle shape of the particles of the inorganic substance (1), 50% volume cumulative diameter (D50) is measured three times using a laser diffraction / scattering type particle size distribution analyzer manufactured by Horiba, Ltd. The average value of the values measured three times may be substituted as the average particle diameter.

The average particle diameter of the particles of the inorganic substance (1) can be adjusted by a conventionally known method, and methods such as dry grinding and wet grinding can be adopted, for example. In dry grinding, for example, a mortar, a jet mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, and a bead mill are suitably used. In wet grinding, various ball mills, high-speed rotary grinders, jet mills, bead mills, ultrasonic homogenizers, high-pressure homogenizers, and the like are suitably used.
For example, in a bead mill, the average particle size can be controlled by adjusting the diameter, type, and mixing amount of beads serving as media.

<Second metal inclusions>
The composition contains at least one selected from the group consisting of an inorganic substance (2) and an organic substance containing a second metal (a second metal-containing substance). The content of the second metal-containing substance in the composition is not particularly limited, but generally, 0.001 to 80% by mass is preferable with respect to the total solid content of the composition. The second metal-containing material may be used alone or in combination of two or more. When using 2 or more types of 2nd metal containing things together, it is preferable that total content is in the said range.

The second metal is different from the first metal. Here, "different" means that the types of metal elements are different.
The form of the second metal-containing substance is not particularly limited, and a second metal single substance (particle), an ion of a second metal, or an inorganic compound containing a second metal (definition of compound: 2 by chemical change) A pure substance that can be divided into a single substance of a species or more elements) or an organic substance may be used, or a mixture thereof may be used; a single metal (particle) of a second metal, a second metal And at least one selected from the group consisting of inorganic substances containing a second metal. The second metal inclusion may be a complex of an inorganic compound and / or an organic compound and a second metal. The complex is, for example, a metal-supported carrier having an inorganic carrier or an organic carrier and a second metal supported on the carrier, or an inorganic compound containing a second metal and the inorganic compound so as to cover the inorganic compound. Preferably, an organic-inorganic composite containing the selected organic compound is used, and in particular, a metal-supported inorganic support having an inorganic support and a second metal supported on the inorganic support is more preferable.

The second metal-containing substance may be a solid or liquid, but the second metal-containing substance is preferably a solid, and particles (as solid) are preferable because they are superior by the effect of the present invention. Those which are present as particles in the composition are preferred.

Among them, the inorganic material (2) is preferable as the second metal-containing material in that the effect of the present invention is more excellent. As the inorganic substance (2), as the form of the first metal in the inorganic substance (1), in addition to the above, one obtained by replacing the first metal in the explanation of the inorganic substance (1) with a second metal can be used.

The second metal is not particularly limited, and silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel and the like can be mentioned, and silver, copper, zirconium or Zinc is preferred, silver, copper or zinc is more preferred, and silver or copper is even more preferred.
Examples of the second metal-containing organic substance include salts of the second metal. As a second metal salt, acetate, acetylacetonate, metal acetylide, (cis, cis-1,5-cyclooctadiene) -1,1,1,5,5,5-hexafluoroacetylacetonate Diethyldithiocarbamate, 7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedionate, lactate, oxalate, perfluorobutyrate, perfluoro Propionates, picrates, propionates, sulfadiazine salts, p-toluenesulfonates, trifluoromethanesulfonates, trifluoroacetates and the like.

As the inorganic carrier of the second metal-supporting inorganic carrier, the same one as the inorganic carrier of the first metal-supporting carrier can be used. In the present specification, the inorganic support of the second metal-supported inorganic support may be referred to as "second inorganic support". Moreover, as an organic carrier of a 2nd metal support organic carrier, a polymer particle is mentioned, for example.
Specific examples of the second metal-supporting inorganic support are preferably metal-supporting zeolite, metal-supporting apatite, metal-supporting glass, metal-supporting zirconium phosphate, or metal-supporting calcium silicate supporting a second metal, with metal-supporting Apatite or metal-loaded glass is more preferable, and metal-loaded glass is even more preferable.

When the second metal-containing material is a particle, the average particle diameter of the second metal-containing material is not particularly limited, but generally, 0.01 μm or more is preferable, 0.05 μm or more is more preferable, and 20 μm or less is preferable, 15 micrometers or less are more preferable.
The measurement and adjustment of the average particle diameter of the second metal-containing particles can be performed using the measurement and adjustment method of the average particle diameter of the particles of the inorganic substance (1) described above.

<Other ingredients>
It is preferable that the said composition contains components other than an inorganic substance (1) and a 2nd metal containing material. As components other than an inorganic substance (1) and a 2nd metal content thing, a solvent, a phosphorus compound, and a hydrophilic component are mentioned. Further, the composition may contain an acidic material, a polymerization initiator, a dispersant, a catalyst, a surfactant, a fragrance, a film-forming agent, an organic antibacterial agent, and the like. Below, each said component is demonstrated.

(solvent)
The composition preferably contains a solvent.
The solvent is not particularly limited and includes water and / or an organic solvent. As the organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenylethyl alcohol, capryl alcohol, lauryl alcohol, and Alcohol solvents such as myristyl alcohol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene Glycol monobutyl ether, diethylene glycol Glycol ether solvents such as butyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; cyclopentane, cyclohexane, methyl Alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether and di-n-butyl ether; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate , Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hex acetate Ester solvents such as ethyl propionate and butyl propionate; hydrophilic solvents such as 10% denatonium alcohol solution, geraniol, octaacetylated sucrose, brucine, linalool, linalyl acetate, and acetic acid; Be The solvents may be used alone or in combination of two or more.

Among them, from the viewpoint of being excellent by the effect of the present invention, the composition preferably contains at least one selected from the group consisting of water and alcohol.
When the composition does not contain alcohol and contains water, the content of water in the composition is not particularly limited, but is preferably 0.01 to 99.999% by mass based on the total mass of the composition. .
When the composition does not contain water but contains alcohol, the content of alcohol in the composition is not particularly limited, but is preferably 0.01 to 99.999% by mass based on the total mass of the composition. .
When the composition contains water and an alcohol, the total content of water and alcohol in the composition is not particularly limited, but is preferably 0.01 to 99.999 mass% with respect to the total mass of the composition. . In this case, the content mass ratio of the alcohol content to the water content (alcohol / water) is not particularly limited, but is preferably 100 to 0.01.

As the alcohol, those described above can be used, but it is more difficult to elute the first metal and the second metal in the solvent, and as a result, ethanol or Isopropyl alcohol is more preferred.

When the composition contains a solvent, the solid content of the composition is not particularly limited, but preferably 0.0001 to 50% by mass based on the total mass of the composition. The solvents may be used alone or in combination of two or more. When two or more solvents are used in combination, the total content is preferably within the above range.

(Inorganics containing a third metal)
The composition preferably contains a third metal-containing inorganic substance (hereinafter, also referred to as “inorganic substance (3)” or “third metal-containing substance”). The content of the inorganic substance (3) in the composition is not particularly limited, but generally 0.0001 to 30% by mass is preferable with respect to the total solid content of the composition.
The third metal contained in the inorganic substance (3) is not particularly limited as long as it is different from any of the first metal and the second metal, but, for example, silver, copper, zinc, mercury, iron, lead, Bismuth, titanium, tin, zirconium, aluminum, nickel and the like can be mentioned, zirconium, aluminum or titanium is preferable, and zirconium is more preferable.
As the inorganic substance (3), one type may be used alone, or two or more types may be used in combination. When two or more phosphorus compounds are used in combination, the total content is preferably within the above range.

The inorganic substance (3) preferably contains a phosphorus atom. The inorganic substance (3) containing a phosphorus atom is not particularly limited, but is a phosphorus having a layered structure in that it is capable of ion exchange of a basic malodorous substance such as ammonia and the like to obtain superior effects of the present invention. Acid metal salts are preferred. Examples of metal phosphates having a layered structure include zirconium phosphate, titanium phosphate, and aluminum trihydrogen phosphate tripolyphosphate. That is, the composition preferably contains at least one phosphorus compound selected from the group consisting of zirconium phosphate, titanium phosphate, and aluminum tripolyphosphate dihydrogen phosphate, and it is more preferable that the composition contains zirconium phosphate. preferable.

(Hydrophilic component)
The above composition preferably contains a hydrophilic component selected from the group consisting of a hydrophilic binder precursor and a hydrophilic binder.
In addition, a hydrophilic binder precursor means the material which can form a hydrophilic binder by hardening reactions, such as a condensation and superposition | polymerization.
Moreover, a hydrophilic binder means the material which can form a hydrophilic film | membrane which can support an inorganic substance (1) and a 2nd metal content thing. When a film made of the above hydrophilic binder is formed on a glass substrate as the hydrophilic binder, for example, one having a water contact angle of 60 ° or less is preferable, and one having a water contact angle of 50 ° or less is preferable. The lower limit of the water contact angle is not particularly limited, but generally 5 ° or more is preferable.
The water contact angle is measured based on the static droplet method of JIS R 3257: 1999. For measurement, FAMMS DM-701 manufactured by Kyowa Interface Science Co., Ltd. is used.

As the hydrophilic component, a silicate compound, a monomer having a hydrophilic group (hereinafter, also referred to as a “hydrophilic monomer”), and a polymer having a hydrophilic group (hereinafter, “the hydrophilic group” are mentioned above, in particular. It is preferable to select at least one selected from the group consisting of “a hydrophilic polymer”.
In addition, the monomer which has a hydrophilic group means the compound which has a hydrophilic group and a polymeric group. The hydrophilic monomer is polymerized to form a hydrophilic polymer when the composition contains a polymerization initiator described later.
Below, a silicate type compound, a hydrophilic monomer, and a hydrophilic polymer are each demonstrated.

-Silicate-based compound In the present specification, a silicate-based compound is a compound selected from the group consisting of a compound in which a hydrolysable group is bonded to a silicon atom, a hydrolyzate thereof, and a hydrolytic condensate thereof, And at least one selected from the group consisting of a compound represented by the following formula (1), a hydrolyzate thereof, and a hydrolytic condensate thereof.
Formula (1) Si- (OR) ₄
In the above formula (1), R represents an alkyl group having 1 to 4 carbon atoms, which may be the same or different.

Examples of the compound represented by the above formula (1) include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra- Examples thereof include t-butyl silicate, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, and propyl butyl silicate.

With the hydrolyzate of the compound represented by Formula (1), the compound obtained by hydrolyzing OR group in the compound represented by Formula (1) is intended. The above hydrolyzate is one in which part of the OR group is hydrolyzed (partial hydrolyzate) even if all of the OR groups are hydrolyzed (completely hydrolyzed) May be That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.
Moreover, the hydrolysis condensation product of the compound represented by Formula (1) is a compound obtained by hydrolyzing OR group in the compound represented by Formula (1), and condensing the obtained hydrolyzate Intended. In the above hydrolytic condensate, even if all OR groups are hydrolyzed and all the hydrolysates are condensed (completely hydrolytic condensate), some OR groups are hydrolysed. It may be decomposed and partially hydrolyzate condensed (partial hydrolytic condensate). That is, the hydrolytic condensate may be a complete hydrolytic condensate, a partial hydrolytic condensate, or a mixture thereof.
The degree of condensation of the hydrolytic condensate is preferably 1 to 100, more preferably 1 to 20, and still more preferably 3 to 15.

The compound represented by Formula (1) will be in the state by which at least one part was hydrolyzed by being mixed with a water component. The hydrolyzate of the compound represented by Formula (1) can be obtained by reacting the compound represented by Formula (1) with a water component to convert the silicon-bonded OR group into a hydroxy group. In the hydrolysis, not all the OR groups need to react, but in order to exhibit hydrophilicity after application, it is preferable that as many OR groups as possible be hydrolyzed. Also, although the minimum amount of water component necessary for hydrolysis is equal to the molar amount of the OR group of the compound represented by the formula (1), a large excess of water is present for the reaction to proceed smoothly. Is preferred.

In addition, although the hydrolysis reaction of the said silicate type compound advances also at room temperature, you may heat for reaction promotion. The longer reaction time is preferable because the reaction proceeds more. Moreover, it is possible to obtain a hydrolyzate even in about half a day in the presence of a catalyst.
In general, the hydrolysis reaction is a reversible reaction, and when water is removed from the system, the hydrolyzate of the silicate compound starts condensation between hydroxy groups. Therefore, when a large excess of water is reacted with the above-mentioned silicate compound to obtain an aqueous solution of hydrolyzate, it is preferable to use the aqueous solution as it is without forcibly isolating the hydrolyzate therefrom.

As a suitable aspect of the said silicate type compound, the compound represented by Formula (X) is mentioned.

Here, in the formula (X), R ¹ to R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms. Also, n represents an integer of 2 to 100.
n is preferably 3 to 15, and more preferably 5 to 10.

As a commercial item of the said silicate type compound, "Ethyl silicate 48" by Korkot company, "MKC silicate MS51" by Mitsubishi Chemical Corporation etc. are mentioned, for example.
The silicate compounds may be used alone or in combination of two or more.

・ Hydrophilic monomer (hydrophilic monomer)
The hydrophilic group is not particularly limited. For example, a polyoxyalkylene group (for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are block or random bond), an amino group And carboxy group, alkali metal salt of carboxy group, hydroxy group, alkoxy group, amido group, carbamoyl group, sulfonamide group, sulfamoyl group, sulfonic acid group, alkali metal salt of sulfonic acid group, and the like. The number of hydrophilic groups in the hydrophilic monomer is not particularly limited, but is preferably 2 or more, more preferably 2 to 6, and even more preferably 2 to 3, from the viewpoint that the obtained film exhibits more hydrophilicity.

The polymerizable group is not particularly limited, and examples thereof include a radically polymerizable group, a cationically polymerizable group, and an anionically polymerizable group. Examples of the radically polymerizable group include a (meth) acryloyl group, an acrylamide group, a vinyl group, a styryl group, and an allyl group. As a cationically polymerizable group, a vinyl ether group, oxiranyl group, and oxetanyl group etc. are mentioned. Among them, a (meth) acryloyl group is preferable as the polymerizable group.
The number of polymerizable groups in the hydrophilic monomer is not particularly limited, but is preferably 2 or more, more preferably 2 to 6, and still more preferably 2 to 3, in that the mechanical strength of the resulting film is more excellent. .

The structure of the main chain of the hydrophilic polymer formed by the polymerization of the hydrophilic monomer is not particularly limited, and examples thereof include polyurethane, poly (meth) acrylate, polystyrene, polyester, polyamide, polyimide, and polyurea.
The hydrophilic monomers may be used alone or in combination of two or more.

(Polymer having hydrophilicity (hydrophilic polymer))
The hydrophilic polymer is not particularly limited, and known polymers can be used. In addition, the definition of a hydrophilic group is as having mentioned above.
Examples of hydrophilic polymers include polymers obtained by polymerizing the above-mentioned hydrophilic monomers. Other than that, for example, a cellulose compound is mentioned. The cellulose-based compound is intended to be a compound having cellulose as a mother core, and examples thereof include carboxymethyl cellulose and nanofibers having triacetyl cellulose as a raw material.
The weight-average molecular weight of the hydrophilic polymer is not particularly limited, but is preferably 1,000 to 1,000,000, and more preferably 10,000 to 500,000, from the viewpoint of better handling such as solubility. In addition, in this specification, a weight average molecular weight is defined as a polystyrene conversion value in a gel permeation chromatography (GPC) measurement.
The hydrophilic polymer may be used alone or in combination of two or more.

The content of the hydrophilic component in the composition is not particularly limited, but is preferably 0.5 to 99.8% by mass, more preferably 1 to 90% by mass, based on the total solid content of the composition. More preferably, it is from 5 to 99% by mass.
The hydrophilic component may be used alone or in combination of two or more. When two or more hydrophilic components are used in combination, the total content is preferably within the above range.

(Acid material)
The composition may contain an acidic material. The content of the acidic material in the composition is not particularly limited, but generally 0.0001 to 50% by mass is preferable with respect to the total mass of the composition. The acidic materials may be used alone or in combination of two or more. When using 2 or more types of acidic materials together, it is preferable that sum total content is in the said range.

When the composition contains an acidic material, basic malodorous substances such as ammonia can be deodorized more efficiently. Among them, it is preferable that the type and amount of the acidic material be selected such that the pH of the composition is 6.5 or less.
As an acidic material, inorganic acids such as phosphoric acid and sulfuric acid; malic acid, lactic acid, tartaric acid, salicylic acid, gluconic acid, adipic acid, phytic acid, fumaric acid, succinic acid, ascorbic acid, sorbic acid, sorbic acid, glyoxylic acid, Meldrum Acids, glutamic acid, picric acid, aspartic acid, acetic acid, formic acid, and organic acids such as citric acid; and the like can be mentioned.
In the present specification, the acidic material is not included in the phosphorus compound.

(Polymerization initiator)
When the composition contains a hydrophilic monomer, the composition preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and known polymerization initiators can be used.
As a polymerization initiator, a thermal polymerization initiator, a photoinitiator, etc. are mentioned, for example.
Examples of the polymerization initiator include benzophenone and aromatic ketones such as phenylphosphine oxide; α-hydroxyalkylphenone compounds (manufactured by BASF, IRGACURE 184, 127, 2959, and DAROCUR 1173); phenylphosphine Oxide compounds (monoacyl phosphine oxide: IRGACURE TPO manufactured by BASF, bisacyl phosphine oxide: IRGACURE 819 manufactured by BASF); and the like.
Among them, a photopolymerization initiator is preferable from the viewpoint of reaction efficiency.

The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 15 parts by mass, and more preferably 1 to 6 parts by mass with respect to 100 parts by mass of the hydrophilic monomer.
The polymerization initiator may be used alone or in combination of two or more. When using 2 or more types of polymerization initiators together, it is preferable that total content is in the said range.

(Dispersant)
The composition preferably contains a dispersant.
The dispersant is not particularly limited, and known dispersants can be used.
The composition preferably contains, as a dispersant, at least one selected from the group consisting of nonionic dispersants and anionic dispersants. From the viewpoint of affinity to the inorganic substance (1) and the second metal-containing substance, a dispersant (anionic dispersant) having an anionic polar group such as a carboxy group, a phosphate group, and a hydroxyl group is more preferable.
A commercial item can be used as an anionic dispersing agent. As a specific example, the trade names DISPERBYK (registered trademark) -110, -111, -116, -140, -161, -162, -163, -164, -170, -170, -171, -174,- Preferred examples include 180, -2012, and -2013. Another example is EFKA-7701, a trade name of BASF.
Further, examples of nonionic dispersants include the trade name DISPERBYK-2010 manufactured by BYK.

Although it does not restrict | limit especially as content of the dispersing agent in the said composition, 20 mass% or less is preferable with respect to the total solid of a composition, 10 mass% or less is more preferable, 8 mass% or less is still more preferable.
The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range.

(catalyst)
When the composition contains a silicate compound, the composition may contain a catalyst that promotes condensation of the silicate compound (hereinafter also referred to as a “reaction catalyst”).

The catalyst is not particularly limited, and examples thereof include alkali catalysts and organometallic catalysts.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide and the like.
Examples of the organic metal catalyst include aluminum chelate compounds such as aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate) And zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate); titanium chelate compounds such as titanium tetrakis (acetylacetonate); and titanium bis (butoxy) bis (acetylacetonate); And organotin compounds such as acetate, dibutyltin dilaurate, and dibutyltin diacrylate.
The type of catalyst is not particularly limited, but an organometallic catalyst is preferable, and among them, an aluminum chelate compound, a titanium chelate compound or a zirconium chelate compound is more preferable, and an aluminum chelate compound is further preferable.

The content of the catalyst is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass, and still more preferably 0.03 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the composition. .
The catalyst may be used alone or in combination of two or more. When two or more types of catalysts are used in combination, the total content is preferably within the above range.

(Surfactant)
The composition may contain a surfactant. The surfactant has the effect of improving the coatability of the composition.
The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
As content of surfactant, 0.001 mass part or more is preferable with respect to 100 mass parts of total solids of a composition. The upper limit of the content of the surfactant is not particularly limited, but 10 parts by mass or less is preferable, 5 parts by mass or less is more preferable, and 4 parts by mass or less with respect to 100 parts by mass of the total solid content of the composition. More preferable.
The surfactant may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that those total content is in the said range.

Examples of nonionic surfactants include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, and polyethylene glycol monostearyl ester.

Examples of the ionic surfactant include anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates and alkyl phosphates; cationic surfactants such as alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts; Amphoteric surfactants such as alkyl carboxy betaines may be mentioned.

(Fragrance)
The composition may contain a flavor.
As a flavor, flavor H-1, H-2, H-3, H-4, H-6, H-9, H-10, H-11, H-12, H-13, H manufactured by Hasegawa Fragrance Co., Ltd. -14, Flavor T-100, T-101, T-102, T-103, T-104, T-105, T-106, T-107, EDA-171 manufactured by Takasago International Corporation Flavor S-201, flavor DA-40 manufactured by Riken Perfume Industries Co., Ltd., etc. may be contained.
The content of the fragrance is, for example, preferably 0.01 to 5% by mass with respect to the total mass of the composition.

(Film-forming agent)
The composition may contain a film-forming agent. In the present specification, the film-forming agent does not include the above-described silicate-based compound, hydrophilic monomer, and hydrophilic polymer.
As a film-forming agent, a thermoplastic resin is mentioned. The film-forming agent functions as a binder, for example, when a film described later is formed.
The thermoplastic resin is preferably a resin having a minimum film-forming temperature of 0 to 35 ° C., and known thermoplastic resins can be used. More specifically, as the thermoplastic resin, polyurethane resin, polyester resin, (meth) acrylic resin, polystyrene resin, fluorine resin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamide imide resin, polyether imide resin, Cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, resin comprising cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic resin A modified polycarbonate resin, and a fluorene ring modified polyester resin etc. are mentioned. Among them, (meth) acrylic resin or urethane resin is preferable.
In addition, a thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.
The content of the thermoplastic resin may be appropriately adjusted according to the type of the thermoplastic resin etc., but for example, 60 mass% or less is preferable and 50 mass% or less is more preferable with respect to the total solid content of the composition. .

In addition to the above, the composition may be organic antibacterial agent, ultraviolet absorber, preservative, pH adjuster, antifoamer, photocatalytic material, filler, antiaging agent, as long as the effects of the present invention can be exhibited. May contain known additives such as additives, antistatic agents, flame retardants, adhesion imparting agents, antioxidants, leveling agents, matting agents, light stabilizers, dyes, pigments, and dispersion stabilizers .
The organic antibacterial agent is not particularly limited. For example, quaternary ammonium salts, phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, pyridine compounds, triazine compounds And benzoisothiazoline compounds and isothiazoline compounds.

<PH of composition>
The pH of the composition is not particularly limited, but is preferably 6.5 or less from the viewpoint of efficiently removing a basic malodorous substance such as ammonia. The pH can be measured using a commercially available pH measurement meter (for example, pH meter HM-30R manufactured by Toa DK K.K.).

<Viscosity of composition>
The viscosity in particular of the said composition is not restrict | limited, It may adjust according to a use.
For example, when applied to coating properties or spray, the viscosity at 25 ° C. of the composition is preferably 300 cP (centipoise: 1 cp = 1 mPa · s) or less, more preferably 200 cP or less, and still more preferably 0.1 to 150 cP.
When the antibacterial and deodorant effects are sustained for a long time, the viscosity at 25 ° C. of the composition is preferably 250 cP or more, more preferably 300 cP or more, and still more preferably 400 cP or more. The upper limit is, for example, 500 cP or less.
The viscosity can be measured using VISCOMETER TUB-10 manufactured by Toki Sangyo Co., Ltd. or SEKONIC VISCOMETER manufactured by Seconik.

<Zeta potential>
The zeta potential of the composition is not particularly limited, but it is preferable to adjust the zeta potential to an appropriate range in consideration of the fact that the particles are appropriately dispersed in the composition to be more excellent in sedimentation resistance. The zeta potential of the above composition is preferably 80 mV to -80 mV, more preferably 70 mV to -70 mV, still more preferably 60 mV to -60 mV.
The zeta potential can be measured using a known method, and a predetermined amount of the dispersion can be introduced into a glass dedicated measuring cell, and measured using ELSZ1 EAS manufactured by Otsuka Electronics Co., Ltd.

<Method of producing composition>
The composition can be prepared by appropriately mixing the above-described essential components and optional components. In addition, the order in particular of mixing of the said component is not restrict | limited.

Second Embodiment of Odor Suppression Method
In the odor suppression method according to the second embodiment of the present invention, a film containing the inorganic substance (1) and the second metal-containing substance is brought into contact with a deodorant containing a specific bacterium to be identified. It is the odor suppression method which suppresses the odor derived from bacteria.

The method for bringing the deodorant into contact with the film is not particularly limited, but typically, the film-coated substrate having the substrate and the film formed on the substrate has already been described. There is a method of contacting odorous substances (eg, urine etc.).
In addition, as the above-mentioned substrate, in addition to the ones already described, the shape is plate-like, film-like, sheet-like, tube-like, fiber-like, particulate or the like, and metal, glass, ceramics and plastics ( The base material which consists of resin etc. can also be used.

〔film〕
The film contains an inorganic substance (1) and a second metal-containing substance. These are the same as the form of the inorganic substance (1) and the second metal-containing substance in the composition described above.
It is preferable that the said film | membrane contains a hydrophilic binder and a phosphorus compound as components other than the above. Moreover, you may contain another component in the range which show the effect of this invention. In addition, the form of a phosphorus compound and other components is the same as that of the form already demonstrated as another component which a composition contains.

<Hydrophilic binder>
The membrane preferably contains a hydrophilic binder. The hydrophilic binder is not particularly limited, and examples thereof include a hydrolyzate of a compound in which a hydrolyzable group is bonded to a silicon atom, a hydrolytic condensate thereof, a polymer having a hydrophilic group, etc. At least one selected from the group consisting of a hydrolyzate of a compound having a degradable group bonded thereto, and a hydrolytic condensate thereof is preferred.
In addition, the preferable form of the compound which the hydrolysable group couple | bonded with the silicon atom, and the preferable form of the polymer which has a hydrophilic group are as having already demonstrated.

<Method of producing membrane>
The film is typically obtained by drying or curing the previously described composition. In addition, when a composition contains a hydrophilic binder precursor as a hydrophilic component, the said film | membrane is obtained by hardening the coating film (composition layer) of a composition. In other words, the film can be obtained by curing the composition layer so that the hydrophilic binder precursor in the composition layer is a hydrophilic binder. On the other hand, when the hydrophilic component in the composition is a hydrophilic binder, it is not necessary to carry out the curing treatment on the composition.

<Film thickness>
The thickness of the film is not particularly limited, but is preferably 0.001 to 50 μm, and more preferably 0.01 to 10 μm.
In addition, with the said film thickness, the sample piece of a film | membrane is embedded in resin, the cross section is cut off with a microtome, and the cross section cut out is observed and measured with a scanning electron microscope. The thickness at any 10 points of the film is measured, and their arithmetically averaged value is intended.

<PH of membrane>
The film surface pH of the film is not particularly limited, but is preferably 6.5 or less, more preferably 5.0 or less, in particular because it is more excellent in the deodorizing property against malodorous substances (odor) such as ammonia and trimethylamine. The following is more preferable. The lower limit of the membrane surface pH of the membrane is not particularly limited, and is, for example, 1.0 or more.
In the present specification, for the film surface pH of the film, 0.02 mL of droplets (pure water) are dropped on the film surface, and after 1 minute, the pH of the droplets is adjusted to the pH of Horiba, Ltd. It is a value determined by measuring using a meter LAQUA F-72.

When the membrane is stored at a low pH, the antimicrobial agent in the membrane may be degraded to reduce the antimicrobial activity. Therefore, for example, when the membrane is applied to applications such as diapers, when the deodorant such as urine adheres to the membrane surface, the membrane surface pH is in the above numerical range (preferably, the membrane surface pH is 6.5 or less) It is preferable that
A specific method is, for example, a method of using an acidic material as an organic acid in a film containing an acidic material. Since the organic acid has low volatility, it adheres to the hydrophilic binder in the dry state. Therefore, when the membrane is in a dry state, the membrane surface pH is maintained near neutral. On the other hand, when the deodorant adheres to the film surface, the organic acid on the film surface is dissolved by the moisture contained in the deodorant, and the film surface pH of the film becomes equal to or less than a predetermined value.
Another method is to use microcapsules composed of a film that is soluble in water or the like and an acidic material contained in the film. When the deodorant adheres to the film surface of the film containing the microcapsules, the film of the microcapsules dissolves to expose the acidic material, and the film surface pH of the film becomes equal to or less than a predetermined value.

Hereinafter, the present invention will be described in more detail based on examples. Materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

Example 1
In a container, while stirring 278 g of ethanol, 152 g of pure water, 9.5 g of a binder which is a siloxane compound ("MKC (registered trademark) Silicate" MS 51 "manufactured by Mitsubishi Chemical Co., Ltd.), aluminum chelate D (aluminum bis (ethyl acetoacetate) Mono (acetylacetonate), ethanol dilution: 15 g solid content concentration, 15 g nonionic surfactant ("Emarex 715" manufactured by Nippon Emulsion Co., pure water dilution: solid content concentration 0.5 mass%), After sequentially adding 10 g of an anionic surfactant (sodium di (2-ethylhexyl) sulfosuccinate, pure water dilution: solid content concentration 0.2% by mass), 15 g of isopropanol, a dispersing agent (manufactured by BYK “DISPERBYK (registration (Trademark)-180 ") 1 g, silver supporting glass (average particle size controlled to 0.6 μm) Chemical dilution, ethanol dilution: solid content 30 mass%, silver supporting glass corresponds to the inorganic substance containing the first metal. 1 g of copper supporting glass (Toagosei Co., Ltd. “NS-20C”, Solid content of 100 mass%, copper-supported glass corresponds to the inorganic substance containing the second metal. 3 g, zirconium phosphate ("NS-10" manufactured by Toagosei Co., Ltd., solid content of 100 mass%, phosphorus The mixture was added with 3 g of the compound, and stirred for 20 minutes to obtain a composition A.
In addition, about the prepared composition, pH at 25 degreeC was measured using the above-mentioned pH meter. The results are shown in Table 1.

The components described in Table 1 were mixed by the same method as in the above Examples, and the solid content was the same as the composition of Example 1 to obtain compositions according to each Example and each Comparative Example. Also, the results of measuring the pH are shown in Table 1. In addition, each composition is a solvent (solvent for dilution) so that content (mass%) of water in a composition and total content (mass%) of alcohol may become as having described in Table 1. Changed the composition of
In addition, each abbreviation in Table 1 represents the following contents.
・ Copper oxide particles: controlled to an average particle diameter of 1 μm of “copper oxide (II)” manufactured by Wako Pure Chemical Industries, Ltd. Silver particles: controlled to an average particle diameter of 1 μm of “silver, powder” manufactured by Wako Pure Chemical Industries, Ltd. Zinc oxide particles: (Wako Pure Chemical Industries "Zinc oxide" controlled to an average particle size of 1 μm)
・ Copper particles / surface organic layer (polystyrene) particles: “Copper, powder” (controlled to an average particle diameter of 1 μm) manufactured by Wako Pure Chemical Industries, Ltd. in THF (tetrahydrofuran) solution of polystyrene having a thiol group at the end for 15 hours Silver particles / surface organic layer (gelatin) particles prepared by immersion and drying: Average particles obtained by drying a solution obtained by mixing an aqueous solution of gelatin with a solution obtained by mixing pure water, an aqueous solution of silver nitrate, and sodium sulfite Copper phthalocyanine prepared by controlling the diameter to 0.3 μm: Wako Pure Chemical Industries "Phthalocyanine copper (II)" controlled to an average particle diameter of 1 μm · "A" in the "Type" column: containing metal Inorganics-"B" in the "Type" column: Metal-containing organic matter-"-": Indicates that the compound was not used.

<Deodorant evaluation>
A non-woven fabric was prepared, and the composition was jetted to the non-woven fabric so that 1 g of the composition of each example and comparative example adhered per 100 cm ^{2 of} non-woven fabric. Next, the obtained non-woven fabric with a composition was dried at 25 ° C. for 2 days to obtain a film-coated substrate. Also, the surface pH of the film obtained by similarly spraying on a PET (polyethylene terephthalate) substrate is shown in Table 1.

Next, 10 g of the urine having an ammonia smell of the odor “E” was sprayed on the above-mentioned film-coated substrate, and left at room temperature. The odors of the sample and the control sample after 10 minutes and 8 hours after standing were smelled by three panelists, and the odor of each sample was evaluated based on the following criteria. (There was no difference in the evaluation results among the three panelists.) The results are shown in the "deodorant" column of Table 1.
In addition, urine (especially urine of patients with urinary tract infections) contains multiple bacteria, and in addition to representative bacteria E. coli and staphylococci, Klebsiella, Citrobacter, Enterobacter, Proteus Bacteria such as genera, pseudomonas, morganella, and Serratia are mixed, and the urine adopted in this evaluation test also has a plurality of bacteria in the same manner.
Therefore, in the present evaluation, the evaluation result after 10 minutes represents the degree of the deodorizing effect to the offensive odor substance originally contained in the urine, and the evaluation result after 8 hours indicates the odor from the above-mentioned bacteria present in the urine. It is considered to represent the degree of the deodorizing effect on the substance.

・ Evaluation criteria "AA": Do not feel odor.
"A": Almost no odor.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": I feel an odor.
"E": strongly smells.

A new membrane-coated substrate different from that used in the above sensory evaluation was described as Escherichia coli (E. coli in the table, "E. coli") according to the evaluation method described in JIS Z 2801: 2012. ), Staphylococcus aureus (Staphylococcus aureus, described in the table as "S. aureus"), and specific bacteria (Klebsiella pneumoniae [K.pneumoniae], Citrobacter freundii [C. freundii], Proteus mirabilis [P. contact time to the bacterial solution obtained by culturing each of mirabilis], Enterobacter cloacae [E. cloacae], Morganella morganii [M. morganii], Pseudomonas aeruginosa [P. aeruginosa], Serratia marcescens [S. marcescens]) The test was performed changing to 8 hours. The antimicrobial activity value after the test was measured and evaluated based on the following evaluation criteria. The results for each bacterial species are shown in the "Antimicrobial" column of Table 1. In Table 1, the genus name of each bacterium is indicated only by initial letters.

Evaluation criteria "AA": The antibacterial activity value was 3.2 or more.
"A": The antimicrobial activity value was 2.2 or more and less than 3.2.
"B": The antimicrobial activity value was 1.5 or more and less than 2.2.
"C": The antimicrobial activity value was 1.0 or more and less than 1.5.
"D": The antimicrobial activity value was less than 1.0.

Table 1 below is divided into three parts of Table 1 (Part 1) to Table 1 (Part 3). The components of each composition and the test results are listed over each row of Table 1 (Part 1) to Table 1 (Part 3). Specifically, the composition of Example 1 contains 0.3 g of silver-supporting glass (the first metal is Ag (silver) and corresponds to an A: metal-containing inorganic substance) as the first metal-containing substance And 3 g of copper-supporting glass (the second metal is Cu (copper) and corresponds to an inorganic substance containing metal) as the second metal-containing substance, and zirconium phosphate as the third metal-containing substance (The third metal is Zr (zirconium) and A corresponds to a metal-containing inorganic substance) 3 g, the water content in the composition is 38% by mass, and the total alcohol content is 59 % By mass, the pH of the composition (liquid) is 6.2, the film surface pH is 6.1, the deodorizing property is "B" after 10 minutes, and "AA" after 8 hours "Antibiotics," AA "against Klebsiella pneumoniae (Klebsiella pneumoniae), Citrobacter freundii Against "AA", against Proteus mirabilis "AA", against "Enterobacter cloacae" "AA", against Pseudomonas aeruginosa (P. aeruginosa) "AA", against "Morganella morganii" "AA", Serratia marcescens “AA” for “A”, “AA” for Escherichia coli (E. coli), and “AA” for Staphylococcus aureus (S. aureus).

From the results shown in Table 1, as shown in Example 1 to Example 15, the inorganic substance containing the first metal, and the inorganic substance containing the second metal different from the first metal, and the second The odor derived from a specific bacterium is suppressed by contacting a composition containing at least one selected from the group consisting of an organic material containing a metal of the present invention with a deodorant containing a specific bacterium It turned out that it can do.
On the other hand, the effects of the present invention were not obtained by the methods of Comparative Examples 1 to 5.

In addition, the method of Example 1 in which the composition contains a metal-supported inorganic support having an inorganic support and a second metal supported on the inorganic support is more excellent than the method of Example 15. It had the effect of the invention.
Also, the method of Example 1 is compared with the method of Example 11 in which the composition contains an inorganic substance containing a second metal, the first metal is silver, and the second metal is copper. Thus, the effects of the present invention were superior.
In addition, the composition contains a metal-containing inorganic substance, and as a metal-containing inorganic substance, a metal-supported inorganic material comprising a first inorganic carrier and silver supported on the first inorganic carrier. The method of Example 1, which comprises a metal-supported inorganic support containing a support and having a second inorganic support and copper supported on the second inorganic support as the second metal-containing inorganic substance, Compared with the method of Example 10, it had the superior effect of the present invention.
Moreover, the composition further contains an inorganic substance containing a third metal different from any of the first metal and the second metal, and the inorganic substance contains a phosphorus atom. As compared with the method of Example 2, it had a superior effect of the present invention.

Claims (37)

1. An inorganic substance containing a first metal, and
   A composition containing at least one selected from the group consisting of an inorganic substance containing a second metal different from the first metal, and an organic substance containing the second metal;
   Contacting a deodorant containing at least one bacterium selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella; The odor control method which suppresses the odor derived from the said bacteria.
2. Metal support comprising an inorganic substance containing the first metal, the single metal of the first metal, an oxide of the first metal, and an inorganic support and the first metal supported on the inorganic support The odor control method according to claim 1, which is at least one selected from the group consisting of inorganic carriers.
3. Metal supported by an inorganic substance containing the second metal, the single metal of the second metal, an oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support The odor control method according to claim 1 or 2, which is at least one selected from the group consisting of inorganic carriers.
4. The composition contains an inorganic material containing the second metal,
   The odor control method according to any one of claims 1 to 3, wherein the first metal is silver and the second metal is copper.
5. The method for suppressing odor according to any one of claims 1 to 4, wherein the composition further contains at least one selected from the group consisting of water and alcohol.
6. The composition contains an inorganic material containing the second metal,
   The inorganic substance containing the first metal is a metal-supported inorganic support having a first inorganic support and silver supported on the first inorganic support, and the inorganic substance containing the second metal is a first metal-supporting inorganic support. The method for suppressing odor according to any one of claims 1 to 5, which is a metal-supported inorganic support having the inorganic support of 2 and copper supported on the second inorganic support.
7. The odor according to any one of claims 1 to 6, wherein the composition further contains an inorganic substance containing a third metal different from any of the first metal and the second metal. How to control.
8. The odor suppression method according to claim 7, wherein the inorganic substance containing the third metal contains a phosphorus atom.
9. The odor control method according to any one of claims 1 to 8, wherein the pH of the composition is 6.5 or less.
10. The method according to any one of claims 1 to 9, wherein the composition further comprises a hydrophilic component selected from the group consisting of a hydrophilic binder precursor and a hydrophilic binder.
11. The odor control method according to claim 10, wherein the hydrophilic component contains at least one selected from the group consisting of a silicate compound, a monomer having a hydrophilic group, and a polymer having a hydrophilic group.
12. The method according to any one of claims 1 to 11, wherein the composition further comprises at least one selected from the group consisting of nonionic dispersants and anionic dispersants.
13. The wiper and the composition having the base fabric impregnated with the base fabric are used to wipe the odorant to bring the composition into contact with the odorant. The odor suppression method as described in any one of these.
14. The composition is sprayed onto the deodorant using a spray having a spray container and the composition stored in the spray container to bring the deodorant into contact with the composition. The odor control method according to any one of claims 1 to 12.
15. An inorganic substance containing a first metal, and
    A film containing at least one selected from the group consisting of an inorganic substance containing a second metal different from the first metal, and an organic substance containing the second metal;
    Contacting a deodorant containing at least one bacterium selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella; The odor control method which suppresses the odor derived from the said bacteria.
16. Metal support comprising an inorganic substance containing the first metal, the single metal of the first metal, an oxide of the first metal, and an inorganic support and the first metal supported on the inorganic support The odor control method according to claim 15, which is at least one selected from the group consisting of inorganic carriers.
17. Metal supported by an inorganic substance containing the second metal, the single metal of the second metal, an oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support The odor control method according to claim 15 or 16, which is at least one selected from the group consisting of inorganic carriers.
18. The film contains an inorganic material containing the second metal;
    The odor control method according to any one of claims 15 to 17, wherein the first metal is silver and the second metal is copper.
19. The film contains an inorganic material containing the second metal;
    The inorganic substance containing the first metal is a metal-supported inorganic support having a first inorganic support and silver supported on the first inorganic support, and the inorganic substance containing the second metal is a first metal-supporting inorganic support. The method for suppressing odor according to any one of claims 15 to 18, which is a metal-supported inorganic support having the inorganic support of 2 and copper supported on the second inorganic support.
20. The odor control according to any one of claims 15 to 19, wherein the film further contains an inorganic substance containing a third metal different from any of the first metal and the second metal. Method.
21. 21. The odor control method according to claim 20, wherein the inorganic substance containing the third metal further contains a phosphorus atom.
22. The odor suppression method according to any one of claims 15 to 21, wherein the pH of the membrane surface of the membrane is 6.5 or less.
23. The odor control method according to any one of claims 15 to 22, wherein the film further comprises a hydrophilic binder.
24. The method according to any one of claims 15 to 23, wherein the film further contains at least one member selected from the group consisting of nonionic dispersants and anionic dispersants.
25. An inorganic substance containing a first metal, and
    An inorganic substance containing a second metal different from the first metal, and at least one selected from the group consisting of an organic substance containing the second metal,
    A composition used to suppress an odor derived from at least one type of bacteria selected from the group consisting of Klebsiella, Citrobacter, Enterobacter, Proteus, Pseudomonas, Serratia, and Morganella.
26. Metal support comprising an inorganic substance containing the first metal, the single metal of the first metal, an oxide of the first metal, and an inorganic support and the first metal supported on the inorganic support The composition according to claim 25, which is at least one selected from the group consisting of inorganic carriers.
27. Metal supported by an inorganic substance containing the second metal, the single metal of the second metal, an oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support The composition according to claim 25 or 26, which is at least one selected from the group consisting of inorganic carriers.
28. Containing an inorganic substance containing the second metal,
    A composition according to any of claims 25 to 27, wherein the first metal is silver and the second metal is copper.
29. The composition according to any one of claims 25 to 28, wherein the composition further contains at least one selected from the group consisting of water and an alcohol.
30. Containing an inorganic substance containing the second metal,
    The inorganic substance containing the first metal is a metal-supported inorganic support having a first inorganic support and silver supported on the first inorganic support, and the inorganic substance containing the second metal is a first metal-supporting inorganic support. The composition according to any one of claims 25 to 29, which is a metal-supported inorganic support having the inorganic support of 2 and copper supported on the second inorganic support.
31. The composition according to any one of claims 25 to 30, wherein the composition further comprises an inorganic substance containing a third metal different from any of the first metal and the second metal. object.
32. 32. The composition of claim 31, wherein the third metal-containing inorganic substance further contains a phosphorus atom.
33. The composition according to any one of claims 25 to 32, having a pH of 6.5 or less.
34. The composition according to any one of claims 25 to 33, further comprising a hydrophilic binder precursor and a hydrophilic component selected from the group consisting of hydrophilic binders.
35. The composition according to any one of claims 25 to 34, wherein the composition further comprises at least one member selected from the group consisting of nonionic dispersants and anionic dispersants.
36. A spray comprising a spray container and the composition according to any one of claims 25 to 35 housed in the spray container.
37. A wiper comprising a backing and the composition according to any one of claims 25 to 35 impregnated in the backing.