JPWO2019013227A1 - Composition, film, base material with film, method for producing base material with film, and modified base material - Google Patents

Abstract

An object of the present invention is to provide a composition capable of forming a film and a modified base material having excellent antibacterial properties and excellent deodorant properties. Another object of the present invention is to provide a film, a base material with a film, a method for producing a base material with a film, and a modified base material. The composition of the present invention is 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 the second metal. And a solvent containing at least one kind of second metal.

Description

  The present invention relates to a composition, a film, a substrate with a film, a method for producing a substrate with a film, and a modified substrate.

An antibacterial film including antibacterial agent particles and a binder is known. The antibacterial film has a function of suppressing the growth of bacteria on its surface.
For example, in Patent Document 1, "1) glass particles, ceramic particles, or porous silica gel particles each having a metal ion having an antibacterial action, and 2) an organosilane capable of hydrolysis and polycondensation or a partial hydrolysis thereof. The composition for an antibacterial coating containing a substance as a main component. "

JP-A-8-27404

  The present inventor has produced and studied an antibacterial film formed by using the antibacterial coating composition described in Patent Document 1, and has revealed that the deodorizing performance does not satisfy the recent required level. ..

Therefore, an object of the present invention is to provide a composition capable of forming a film or a modified substrate having excellent antibacterial properties and excellent deodorant properties.
Moreover, this invention also makes it a subject to provide a film | membrane, the base material with a film, the manufacturing method of a base material with a film, and a modified base material.

  The present inventor, as a result of diligent study to achieve the above-mentioned object, found that the object can be achieved by the following configuration.

[1] An inorganic material containing a first metal,
A component containing at least one second metal 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;
And a solvent.
[2] The inorganic substance containing the first metal has a simple substance of the first metal, an oxide of the first metal, and an inorganic carrier and the first metal supported on the inorganic carrier. The composition according to [1], which is at least one selected from the group consisting of metal-supporting inorganic carriers.
[3] The inorganic material containing the second metal has a simple substance of the second metal, an oxide of the second metal, and an inorganic carrier and the second metal supported on the inorganic carrier. The composition according to [1], which is at least one selected from the group consisting of metal-supporting inorganic carriers.
[4] The composition according to any one of [1] to [3], wherein the component containing the second metal is an inorganic substance containing the second metal.
[5] The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and one of the inorganic substance containing the first metal and the inorganic substance containing the second metal is either Has an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, or is either an inorganic material containing the first metal or an inorganic material containing the second metal. The composition according to [4] also has an average particle size of 0.9 μm or less.
[6] The composition according to any one of [1] to [5], wherein the first metal is silver and the second metal is copper.
[7] The inorganic substance containing the first metal is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier, [1] to [6] The composition according to any of the above.
[8] The inorganic substance containing the second metal is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, [1] to [7] The composition according to any of the above.
[9] The composition according to [7], wherein the first inorganic carrier is glass.
[10] The composition according to [8], wherein the second inorganic carrier is glass.
[11] The inorganic material containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic material containing the second metal is a glass and a glass. The composition according to any one of [4] to [6], which is a copper-supporting glass having supported copper.
[12] The composition according to any one of [1] to [11], further containing a hydrophilic component selected from the group consisting of a hydrophilic binder precursor and a hydrophilic binder.
[13] The composition according to [12], 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.
[14] An inorganic material containing a first metal,
A component containing at least one second metal 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. Yes, the membrane.
[15] The inorganic substance containing the first metal has a simple substance of the first metal, an oxide of the first metal, and an inorganic carrier and the first metal supported on the inorganic carrier. The membrane according to [14], which is at least one selected from the group consisting of metal-supporting inorganic carriers.
[16] The inorganic substance containing the second metal has a simple substance of the second metal, an oxide of the second metal, and an inorganic carrier and the second metal supported on the inorganic carrier. The membrane according to [14], which is at least one selected from the group consisting of metal-supporting inorganic carriers.
[17] The film according to any one of [14] to [16], wherein the component containing the second metal is an inorganic substance containing the second metal.
[18] The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and one of the inorganic substance containing the first metal and the inorganic substance containing the second metal is Has an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, or is either an inorganic material containing the first metal or an inorganic material containing the second metal. The film according to [17] also has a mean particle size of 0.9 μm or less.
[19] The film according to any one of [14] to [18], wherein the first metal is silver and the second metal is copper.
[20] In the above [14] to [19], the inorganic substance containing the first metal is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier. The membrane according to any one.
[21] The inorganic substance containing the second metal is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, [14] to [20] The membrane according to any one.
[22] The film according to [20], wherein the first inorganic carrier is glass.
[23] The film according to [21], wherein the second inorganic carrier is glass.
[24] The inorganic substance containing the first metal is a silver-loaded glass having glass and silver supported on the glass, and the inorganic substance containing the second metal is a glass and a glass. The film according to any one of [17] to [19], which is a copper-supporting glass having supported copper.
[25] The film according to any one of [14] to [24], which further contains a hydrophilic binder.
[26] The hydrophilic binder is at least one selected from the group consisting of a hydrolyzate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a hydrolytic condensate thereof, or a hydrophilic polymer. 25].
[27] A substrate with a film, comprising the substrate and the film according to any one of [14] to [26].
[28] A step of forming a composition layer by applying the composition according to any one of [1] to [13] containing a hydrophilic binder precursor to the surface of a substrate to form a composition layer,
And a step of curing the composition layer to obtain a film.
[29] A method for producing a substrate with a film, which comprises a step of forming a film by applying the composition according to any one of [1] to [13] containing a hydrophilic binder to the surface of the substrate. ..
[30] A base material, an inorganic material containing a first metal, which is disposed on or inside the base material, and an inorganic material containing a second metal different from the first metal, and the above And a component containing at least one second metal selected from the group consisting of organic substances containing a second metal.
[31] A base material, an inorganic material containing a first metal, which is disposed on or inside the base material, and an inorganic material containing a second metal different from the first metal, and the above A modified base material comprising a hydrophilic binder and a component containing at least one second metal selected from the group consisting of organic substances containing a second metal.
[32] The inorganic substance containing the first metal has a simple substance of the first metal, an oxide of the first metal, and an inorganic carrier and the first metal supported on the inorganic carrier. The modified substrate according to [30] or [31], which is at least one selected from the group consisting of metal-supporting inorganic carriers.
[33] The inorganic substance containing the second metal has a simple substance of the second metal, an oxide of the second metal, and an inorganic carrier and the second metal supported on the inorganic carrier. The modified substrate according to [30] or [31], which is at least one selected from the group consisting of metal-supporting inorganic carriers.
[34] The modified substrate according to any one of [30] to [33], wherein the component containing the second metal is an inorganic substance containing the second metal.
[35] The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and one of the inorganic substance containing the first metal and the inorganic substance containing the second metal is either Has an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, or is either an inorganic material containing the first metal or an inorganic material containing the second metal. The modified base material according to [34], having an average particle size of 0.9 μm or less.
[36] The modified substrate according to any one of [30] to [35], wherein the first metal is silver and the second metal is copper.
[37] In the above [30] to [36], the inorganic substance containing the first metal is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier. The modified base material according to any one of claims.
[38] The inorganic material containing the second metal is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, [30] to [37] The modified base material according to any one of claims.
[39] The modified substrate according to [37], wherein the first inorganic carrier is glass.
[40] The modified substrate according to [38], wherein the second inorganic carrier is glass.
[41] The inorganic material containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic material containing the second metal is a glass and a glass. The modified base material according to any one of [34] to [36], which is a copper-supported glass having supported copper and supported copper.

  According to the present invention, it is possible to provide a composition capable of forming a film or a modified substrate having excellent antibacterial properties and excellent deodorant properties. Moreover, according to this invention, a film | membrane, the base material with a film, the manufacturing method of a base material with a film, and a modified base material can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the notation of group (atom group) in the present specification, notation indicating neither substitution nor non-substitution means not having a substituent but having a substituent as long as the effects of the present invention are not impaired. It also includes. For example, an “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). This has the same meaning for each compound.
In addition, in the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acrylic” represents both or both of acrylic and methacrylic, and “(meth) ) “Acryloyl” means both acryloyl and / or methacryloyl.
In addition, in the present specification, the numerical range represented by using "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.

〔Composition〕
The composition (hereinafter also referred to as “composition according to the embodiment”) is an inorganic material containing the first metal (hereinafter also referred to as “inorganic material (1)” or “first metal-containing material”), and the above. At least one selected from the group consisting of an inorganic substance containing a second metal different from the first metal (hereinafter also referred to as "inorganic substance (2)") and an organic substance containing the second metal. It contains a component containing the second metal (hereinafter, also referred to as “second metal-containing material”) and a solvent.
In the present specification, the term “metal” simply includes a metal simple substance (metal simple substance particles), a metal ion, and a metal atom contained in a compound.

  The film or modified substrate formed from the composition has excellent antibacterial properties and deodorant properties due to the presence of the inorganic substance (1) and the second metal-containing material.

Further, as will be described later, the second metal-containing material is an inorganic material (2), and at least one selected from the group consisting of the inorganic material (1) and the inorganic material (2) is in the form of particles, and the average thereof. When the particle size is 1.2 μm or less, a film or modified substrate having better antibacterial properties and better deodorant properties can be obtained.
In particular, as described below, the inorganic substance (1) is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier, and the inorganic substance (2 Is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, a film or a modifying group having better antibacterial properties and better deodorant properties. The material is obtained. Regarding urine odor, for example, in the urine odor generating mechanism, an enzyme generated from a bacterium decomposes urea and becomes an ammonia source, but copper is presumed to exhibit excellent enzyme decomposing ability and exhibits a high deodorizing ability. On the other hand, silver is known to exhibit high antibacterial properties. Therefore, when the film or the modified base material contains the silver-supporting inorganic carrier and the copper-supporting inorganic carrier, it is presumed that the antibacterial property and the deodorizing property are more excellent. Further, it is known that copper exhibits not only high deodorizing ability but also high antibacterial activity as described above, but the present inventor has conducted various studies to find that silver and copper have different mechanisms from each other. It is speculated that it exhibits antibacterial properties. As a result, when the membrane or the modified substrate contains a silver-supporting inorganic carrier and a copper-supporting inorganic carrier, the two antibacterial mechanisms of copper and silver simultaneously act on the bacterium, and By comparison, it is thought that a remarkably excellent antibacterial property can be obtained.
Furthermore, the inorganic carrier in at least one of the silver-supported inorganic carrier and the copper-supported inorganic carrier (preferably a copper-supported inorganic carrier, more preferably a silver-supported inorganic carrier and a copper-supported inorganic carrier) is amorphous. In such a case, the metal ions are more easily released from the first metal and the second metal, so that the above-described effect is further excellent.

The use of the above composition is not particularly limited, but it can be applied to, for example, diapers used in nursing care sites, and exhibits excellent antibacterial effect and deodorant effect against urine odor.
Urine odor is caused by substances such as ammonia and trimethylamine contained in urine. When the urine absorbed in the diaper is left for a long time, the substances causing the urine odor further increase due to the action of bacteria, and the odor of the diaper becomes stronger.
On the other hand, when the film formed by the composition is formed at the site where urine / feces in the diaper comes into contact, bacterial growth and enzymatic decomposition of the urine / feces substance by the bacteria are suppressed, so that the above-mentioned ammonia and trimethylamine The increase of substances such as That is, the increase in odor is suppressed. Furthermore, the deodorizing effect is stably maintained for a long time after the urine is absorbed in the diaper.
Note that the above effects can be similarly obtained by the modified base material described below, which is formed using the above composition.
Below, each component contained in the said composition is explained in full detail.

<Inorganic substance (1)>
The inorganic substance (1) is not particularly limited, but includes Escherichia (eg, E.coli), Staphylococcus (eg, S.aureus), Klebsiella (eg, K.oxytoca, K.pneumoniae), Serratia (eg, S. marcescens), Citrobacter (eg, C.freundii, C.diversus, etc.), Enterobacter (eg, E.aerogenes, E.cloacae), Proteus (eg, P.mirabilis, P. vulgaris etc.), Pseudomonas genus (eg P. aeruginosa etc.), and Morganella genus (eg M. morganii etc.) bacteria having sterilization (including sterilization) and / or bacteriostatic effect preferable.

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

The inorganic material (1) contains the first metal. The form of the inorganic substance (1) is not particularly limited, and a simple substance of the first metal (particles of a simple metal), an ion of the first metal, and an inorganic compound containing the first metal (definition of compound: depending on chemical change) It refers to a pure substance that can be divided into two or more kinds of elements), or a mixture thereof. The inorganic substance (1) may be a composite of an inorganic compound and a first metal. As the composite, for example, an inorganic carrier and a first metal supported on the inorganic carrier (for example, a simple substance of the first metal (a simple metal particle), an ion of the first metal, and a first metal are included. Any of the compounds contained therein (specifically, the compound containing the first metal may be an inorganic compound containing the first metal). Hereinafter, also referred to as "first metal-supporting inorganic carrier").
Among them, from the viewpoint that the effect of the present invention is more excellent, the inorganic substance (1) is a simple substance (particle) of the first metal, an ion of the first metal, an oxide of the first metal, and a first metal-carrying inorganic substance. At least one selected from the group consisting of carriers is preferable, and at least one selected from the group consisting of a simple substance (particles) of the first metal, an oxide of the first metal, and a first metal-supporting inorganic carrier. More preferably, the first metal-supporting inorganic carrier is still more preferable.

The first metal is not particularly limited, but examples thereof include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, and nickel. Among them, silver, copper, zinc, Aluminum or zirconium is preferable, silver, copper, zinc or aluminum is more preferable, silver or copper is further preferable, and silver is particularly preferable.
The inorganic substance (1) may be, for example, a first metal oxide, a nitride, a halide, a cyanide, a selenide, a sulfide, a telluride, a salt of the first metal, or the like.
Examples of the salt of the first metal include arsenate, hydrogen fluoride, bromate, chlorate, chromate, cyanate, hexafluoroantimonate, hexafluoroarsenate and hexafluoro. Phosphate, iodate, isothiocyanate, molybdate, nitrate, nitrite, perchlorate, permanganate, perrhenate, phosphate, selenate, selenite, sulfuric acid Examples thereof include salts, sulfites, tetrafluoroborates, tetratungstates, thiocyanates, vanadates and the like.

The type of the inorganic carrier of the first metal-supporting inorganic carrier is not particularly limited, but zinc calcium phosphate, calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicate, activated alumina, silicon oxide, silicate glass, borosilicate Salt glass, phosphate glass, zeolite (crystalline aluminosilicate salt), apatite, hydroxyapatite, titanium phosphate, potassium titanate, hydrous bismuth oxide, hydrous zirconium oxide, and hydrotalcite; activated carbon; metal; and the like. Be done.
In addition, in this specification, the inorganic carrier of the first metal-supporting inorganic carrier may be referred to as “first inorganic carrier”.

  The inorganic carrier may be crystalline or amorphous (amorphous), but is preferably amorphous and more preferably glass. Examples of the material that can form the glass include silicates, borosilicates, and phosphates. Of these, silicates are preferable, and aluminum silicate is more preferable.

The aluminum silicate may be a natural product or a synthetic product. As the aluminum silicate, a compound represented by the following formula (A) is preferable.
Al ₂ O ₃ · nSiO ₂ · mH ₂ O (A)
In the formula (A), n is a positive number of 6 or more (preferably 6 to 50), and m is a positive number of 1 to 20. Especially, it is preferable that n is 8-15 and m is 3-15.

  The inorganic substance (1) includes, among the above inorganic carriers, silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel and the like (for example, zirconium phosphate and Aluminum silicate etc.) can also be used.

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

When the inorganic substance (1) is particles, the average particle size of the particles of the inorganic substance (1) is not particularly limited, but is generally 0.01 μm or more, and preferably 0.2 μm or more. The upper limit is not particularly limited, but is, for example, 10 μm or less, preferably 5.0 μm or less. Among them, 3.0 μm or less is preferable, 1.5 μm or less is more preferable, 1.2 μm or less is further preferable, 0.9 μm or less is further preferable, 0.6 μm or less is particularly preferable, and 0.5 μm or less is most preferable. , 0.3 μm or less is more preferable.
When the sedimentation property and the transparency of the composition are taken into consideration, the smaller the average particle size of the inorganic substance (1), the more the dispersibility is improved, and as a result, the transparency of the composition tends to be high. The average particle size of the inorganic material (1) is preferably 0.5 μm or less, more preferably 0.4 μm or less, from the viewpoint that the transparency of the composition is more excellent.

The average particle size of the particles of the inorganic substance (1) can be measured by observing with an electron microscope. Specifically, the average particle size is the primary particle and the secondary particle of the inorganic substance (1) (the “secondary particle” is an aggregate formed by fusing or contacting the primary particles with each other). Is measured from the image of the electron microscope, and the number of particles on the side with the smallest diameter is 5% and the number of particles on the side with the largest diameter is 5%, which is 90%. It is a value obtained by averaging the diameters of particles in the range. That is, the average particle size is a value obtained from the primary particles and the secondary particles. Further, the diameter means a diameter corresponding to a circumscribing circle of particles.
In addition, when there is no significant difference in the particle shape of the particles of the inorganic substance (1), the 50% volume cumulative diameter (D50) is measured three times using a laser diffraction / scattering type particle size distribution measuring device manufactured by Horiba Ltd. You may substitute the average value of the value measured 3 times as an average particle diameter.

  When the average particle size of the inorganic material (1) is within the above numerical range, the inorganic material (1) is exposed from the hydrophilic binder in the film or modified substrate formed using the composition containing the hydrophilic binder described below. It is easy to be fixed in the state. Therefore, for example, when the inorganic substance (1) is a metal-supporting carrier, the metal is more easily released from the carrier, and the effect of the present invention is more excellent.

The inorganic material (1) may be formed by either a breakdown method (for example, a crushing method) or a build-up method.
Examples of the pulverization method of the inorganic material (1) include dry pulverization and wet pulverization. In the dry pulverization, for example, a mortar, a jet mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, a bead mill, etc. are appropriately used. Further, in wet pulverization, various ball mills, high-speed rotary pulverizers, jet mills, bead mills, ultrasonic homogenizers, high-pressure homogenizers, etc. are appropriately used. For example, in a bead mill, the average particle size can be controlled by adjusting the diameter, type, and mixing amount of beads as media.

The build-up method is a method of directly forming the inorganic substance (1), for example, by mixing a raw material component such as a hydroxide and an organometallic substance and an arbitrary component and carrying out a reaction.
The build-up method may be a batch method in which the raw material components are added to the pod and stirred and mixed, or a method in which the raw material components are continuously mixed and reacted in the flow path (for example, a microreactor or a double tube). A mixed method) may be used, but the latter is preferable.

As the inorganic substance (1), one type may be used alone, or two or more types may be used in combination.
The content of the inorganic material (1) in the above composition (the total content when a plurality of inorganic materials (1) are contained) is not particularly limited, but is 0.001 to 55 mass with respect to the total solid content of the composition. % Is preferable, 0.001 to 50 mass% is more preferable, and 0.01 to 40 mass% is further preferable.

  Further, the content of the metal in the inorganic substance (1) is not particularly limited. For example, when the inorganic substance (1) is a metal-supporting carrier, the content of the metal is 0.001 to 0.001 to the total mass of the metal-supporting carrier. 30 mass% is preferable, and 0.01-10 mass% is more preferable. When the composition contains a plurality of inorganic substances (1), the total metal content is preferably within the above numerical range.

<Second metal inclusion>
The composition contains at least one kind (second metal-containing material) selected from the group consisting of an inorganic material (2) and an organic material containing a second metal.

The content of the second metal-containing material in the composition is not particularly limited, but is preferably 0.01 to 50% by mass, preferably 0.01 to 40% by mass, more preferably 0.1 to 35% by mass, 0.1 to 30 mass% is more preferable, and 0.1 to 10 mass% is particularly preferable.
The second metal-containing material may be used alone or in combination of two or more. When two or more second metal-containing substances are used in combination, the total content is preferably within the above range.

  The second metal is different than the first metal. Here, "different" means that the types of metal elements are different.

  The second metal is not particularly limited, and examples thereof include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, and nickel. Silver, copper, zinc, aluminum, or Zirconium is preferred, silver, copper, zinc, or aluminum is more preferred, and copper is even more preferred.

The form of the inorganic substance (2) is not particularly limited, and may be any of a simple substance (particles) of the second metal, an ion of the second metal, or an inorganic compound containing the second metal, and a mixture thereof. May be The inorganic substance (2) may be a composite of an inorganic compound and a second metal. The composite includes, for example, an inorganic carrier and a second metal (a simple substance of the second metal (a simple metal particle), an ion of the second metal, and a second metal supported on the inorganic carrier. And a compound (specifically, the compound containing the second metal may be an inorganic compound containing the second metal). Also referred to as "second metal-supporting inorganic carrier").
The inorganic substance (2) is at least one selected from the group consisting of a simple substance (particles) of the second metal, an oxide of the second metal, and a second metal-supporting inorganic carrier from the viewpoint of being more excellent in the effect of the present invention. Is more preferable, and a second metal-supporting inorganic carrier is still more preferable.

  As the inorganic carrier of the second metal-supporting inorganic carrier, the same carrier as that described as the inorganic carrier of the first metal-supporting inorganic carrier can be used. In addition, in this specification, the inorganic carrier of the second metal-supporting inorganic carrier may be referred to as a “second inorganic carrier”.

  The inorganic carrier may be crystalline or amorphous (amorphous), but is preferably amorphous and more preferably glass. Examples of the material that can form the glass include silicates, borosilicates, and phosphates. Of these, silicates are preferable, and aluminum silicate is more preferable.

  Specific examples of the second metal-supporting inorganic carrier include metal-supporting zeolite, metal-supporting apatite, metal-supporting glass, metal-supporting zirconium phosphate, or metal-supporting calcium silicate on which a second metal is supported, and metal-supporting glass. Is more preferable.

  In addition, as the inorganic substance (2), among the above-mentioned inorganic carriers, those containing silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel and the like (for example, zirconium phosphate and Aluminum silicate etc.) can also be used.

  Examples of the organic substance containing the second metal include salts of the second metal. Examples of the salt of the second metal include 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 Examples thereof include propionate, picrate, propionate, sulfadiazine salt, p-toluenesulfonate, trifluoromethanesulfonate, trifluoroacetate and the like.

Further, the organic substance containing the second metal may be a complex of an organic compound and the second metal. The composite includes, for example, an organic carrier and a second metal (a simple substance of the second metal (a simple metal particle), an ion of the second metal, and a second metal supported on the organic carrier. Any of a compound (specifically, the compound containing the second metal may be an inorganic compound containing the second metal). An organic-inorganic composite containing an inorganic compound containing the second metal and an organic compound arranged so as to cover the inorganic compound is preferable. Among them, a metal containing an organic carrier and a second metal supported on the organic carrier. A supported organic carrier (hereinafter, also referred to as “second metal-supported organic carrier”) is more preferable.
Examples of the organic carrier of the second metal-supporting organic carrier include polymer particles.

Specific examples of the second metal-supporting organic carrier include, for example, polymer particles supporting a second metal selected from the group consisting of copper particles and copper oxide particles (hereinafter, also referred to as “copper-supporting polymer”). Can be mentioned.
The average particle size of the copper particles and the copper oxide particles is preferably 90 nm or less, more preferably 70 nm or less, and further preferably 50 nm or less, from the viewpoint that the effect of the present invention is more excellent. The lower limit is not particularly limited, but is 1 nm or more, for example.
As for the average particle diameter of the copper particles and the copper oxide particles, the method for measuring the average particle diameter of the inorganic substance (1) particles described above can be used.
Incidentally, from the image of the electron microscope, with copper particles or copper oxide particles in the copper-supported polymer particles, and a state in which only copper particles or copper oxide particles are dispersed, if there is no significant change in particle shape, copper particles or copper oxide The average particle size may be substituted by a value measured by dynamic light scattering using a dispersion liquid of only particles. In this case, the average particle size can be measured by dynamic light scattering using a particle size distribution measuring device using laser diffraction.

In the copper-supporting polymer particles, the average primary particle diameter of the copper particles and the copper oxide particles is preferably less than 100 nm. The lower limit is not particularly limited, but is 1 nm or more, for example. The average primary particle diameter of the copper particles and the copper oxide particles is preferably 5 to 90 nm, more preferably 5 to 50 nm, from the viewpoint that the effect of the present invention is more excellent.
In addition, the "average primary particle size" means that the diameter of each primary particle is measured from an image of an electron microscope, and the primary particle number 5% is the smallest diameter side among the total primary particle numbers and the largest diameter side. It is a value obtained by averaging the diameters of primary particles in the range of 90% excluding 5% of the primary particles. Here, the diameter means a diameter corresponding to a circumscribed circle of the primary particles.

Moreover, in the said copper carrying | support polymer particle, 100-1000 nm is preferable and, as for the average particle diameter of the said polymer particle, 100-800 nm is more preferable.
As the average particle size of the polymer particles, the method for measuring the average particle size of the inorganic substance (1) particles described above can be used.
The resin material constituting the polymer particles is not particularly limited, and among them, polyurethane resin, (meth) acrylic resin, polystyrene resin, polystyrene- (meth) acrylic copolymer resin, or polyolefin resin is preferable. As the polymer particles, for example, Eposter 050W and 100W manufactured by Nippon Shokubai can be used.

  In the copper-supported polymer particles, the ratio of the polymer particles to the copper particles and the copper oxide particles (mass of the polymer particles / total mass of the copper particles and the copper oxide particles) is not particularly limited, but the antibacterial property is more excellent. In terms of mass ratio, for example, the range of 1 / 0.00001 to 1/100000 is preferable, and the range of 1 / 0.0001 to 1/10000 is more preferable.

  Further, the copper-supporting polymer particles may have a coating film made of a silane compound formed on at least a part of the surface of the polymer particles as a carrier. The silane compound is obtained, for example, by condensing a silicate compound described below.

  The second metal-containing material may be a solid material or a liquid material, but the second metal-containing material is preferably a solid material in terms of being excellent in the effect of the present invention, and as the solid material, particles ( Those present as particles in the composition) are preferred.

  As the second metal-containing material, the inorganic substance (2) and the second metal-supporting organic carrier are preferable. The second metal-supporting inorganic carrier or the second metal-supporting organic carrier is more preferred, and the second metal-supporting inorganic carrier is still more preferred.

When the second metal-containing material is particles, the average particle diameter of the second metal-containing material is not particularly limited, but is, for example, 4.0 μm or less, preferably 2.0 μm or less, and more preferably 1.5 μm or less. preferable. The average particle diameter of the second metal-containing material is preferably 1.2 μm or less, more preferably 1.0 μm or less, still more preferably 0.9 μm or less, still more preferably 0.7 μm or less, and 0.6 μm or less. Is particularly preferable, 0.5 μm or less is the most preferable, 0.3 μm or less is the most preferable, 0.2 μm or less is the most preferable, and 0.15 μm or less is the most preferable. The lower limit is preferably 0.01 μm or more, more preferably 0.10 μm or more.
The measurement and adjustment of the average particle diameter of the particles of the second metal-containing material can be performed by the method of measurement and adjustment of the average particle diameter of the particles of the inorganic material (1) described above.

When the second metal-containing material is particles, the aspect ratio is not particularly limited, but is preferably 1 to 40, more preferably 2 to 20.
The aspect ratio is calculated by the following method. First, using an electron microscope, of the two parallel straight lines circumscribing the second metal inclusion, select the two parallel straight lines that maximize the distance between the straight lines and determine the distance between the two parallel straight lines. The major axis of the second metal-containing material. Next, of the two parallel straight lines that are orthogonal to the long axis and circumscribe the second metal inclusion, select the two parallel straight lines that have the smallest distance between the straight lines, and select between the two parallel straight lines. Is the short axis of the second metal-containing material. The ratio of the major axis to the obtained minor axis (major axis / minor axis) is defined as the specific aspect ratio. This aspect ratio can be obtained by performing this operation on any 100 or more second metal inclusions and arithmetically averaging the obtained specific aspect ratios.

  As an example of a suitable form of the composition, the inorganic material (2) is contained as the second metal-containing material, both the inorganic material (1) and the inorganic material (2) are particles, and the inorganic material (1) and the inorganic material ( The average particle size of each of 2) is preferably 1.5 μm or less, and the average particle size of each of the inorganic substance (1) and the inorganic substance (2) is more preferably 1.2 μm or less. ) And the inorganic substance (2) have an average particle diameter of 1.2 μm or less, and the other average particle diameter of 0.9 μm or less is more preferable, and the average particle diameter of the inorganic substance (1) and the inorganic substance (2) is Either one has an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, or the average particle size is 0 for both the inorganic substance (1) and the inorganic substance (2). It is particularly preferable that the average particle size of both the inorganic substance (1) and the inorganic substance (2) is 0.5 μm or less, and it is particularly preferable that the average particle size of the inorganic substance (1) and the inorganic substance (2) is 0.5 μm or less. Most preferably, the average particle size of one is 0.5 μm or less, and the average particle size of the other is 0.3 μm or less, and the average particle size of both inorganic substance (1) and inorganic substance (2) is 0.3 μm. The following is more preferable.

  As another example of a suitable form of the composition, a form containing a silver-containing material as the inorganic substance (1) and a copper-containing material as the second metal-containing material can be mentioned. In the above composition, the mass ratio of the content of copper in the copper-containing material to the content of silver in the silver-containing material (content of copper in the copper-containing material / The content of silver in the silver-containing material) is, for example, preferably 800 or less, more preferably 350 or less, further preferably 300 or less, preferably 0.1 or more, and more preferably 5.0 or more.

When the composition contains a silver-containing material as the inorganic substance (1) and a copper-containing material as the second metal-containing material, both the silver-containing material and the copper-containing material are particles from the viewpoint of deodorant property and antibacterial property. It is preferable that both the silver-containing material and the copper-containing material have an average particle diameter of 1.5 μm or less, and the silver-containing material and the copper-containing material both have an average particle diameter of 1.2 μm or less. More preferably, one of the silver-containing material and the copper-containing material has an average particle diameter of 1.2 μm or less, and the other has an average particle diameter of 0.9 μm or less. Either one has an average particle diameter of 1.2 μm or less and the other has an average particle diameter of 0.6 μm or less, or both of the silver-containing material and the copper-containing material have an average particle diameter of 0. It is particularly preferable that the average particle diameter of the silver-containing material and the copper-containing material is 0.5 µm or less, and the average particle diameter of either one of the silver-containing material and the copper-containing material is particularly preferable. Is 0.5 μm or less, and the other average particle size is most preferably 0.3 μm or less, and most preferably the average particle size of both the silver-containing material and the copper-containing material is 0.3 μm or less. preferable.
In the above aspect, the silver-containing material as the inorganic substance (1) is preferably a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier, and more preferably silver-supporting glass. Further, the copper-containing material as the second metal-containing material is supported on the copper-supporting inorganic carrier having a second inorganic carrier and the copper supported on the second inorganic carrier, and on the organic carrier and the organic carrier. One or more selected from the group consisting of a copper-supporting organic carrier having copper, and a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier is more preferred.

  Further, as another preferred embodiment of the above composition, a silver-supporting inorganic carrier is included as the inorganic material (1), and a copper containing material (preferably, the second inorganic carrier and the above-mentioned second inorganic carrier are contained as the second metal containing material). 2 or more selected from the group consisting of a copper-supporting inorganic carrier having copper supported on an inorganic carrier, and a copper-supporting organic carrier having an organic carrier and copper supported on the organic carrier, More preferably, a form including a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier) and zirconium phosphate can be mentioned.

Moreover, as an example of a suitable form of the said composition, the said inorganic substance (1) is a silver carrying | support inorganic carrier, and the form in which a 2nd metal content is zirconium phosphate or phosphate glass is mentioned.
In the case of the above mode, the average particle size of the inorganic material (1) is preferably 0.01 μm or more, more preferably 0.2 μm or more, further preferably 0.3 μm or more, particularly preferably 0.5 μm or more, and 10 μm or less. It is preferably 5.0 μm or less. The average particle size of the second metal-containing material is preferably 4.0 μm or less, more preferably 2.0 μm or less, further preferably 1.5 μm or less, particularly preferably 1.0 μm or less, most preferably 0.5 μm or less. , 0.01 μm or more is preferable, and 0.1 μm or more is more preferable. Among them, the average particle size of both the inorganic substance (1) and the second metal-containing material is preferably 0.9 μm or less (preferably 0.6 μm or less, more preferably 0.5 μm or less).

Moreover, as an example of a suitable form of the said composition, the said inorganic substance (1) is a zirconium phosphate or phosphate glass, and a 2nd metal containing material is a copper containing material (preferably a 2nd inorganic carrier and One or more selected from the group consisting of a copper-supporting inorganic carrier having copper supported on the second inorganic carrier, and a copper-supporting organic carrier having organic carrier and copper supported on the organic carrier. And more preferably, a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier).
In the case of the above mode, the average particle size of the inorganic substance (1) is preferably 4.0 μm or less, more preferably 2.0 μm or less, further preferably 1.5 μm or less, particularly preferably 1.0 μm or less, and 0.5 μm The following is most preferable, 0.01 μm or more is preferable, and 0.1 μm or more is more preferable. The average particle size of the second metal-containing material is preferably 0.01 μm or more, more preferably 0.2 μm or more, further preferably 0.3 μm or more, particularly preferably 0.5 μm or more, and preferably 10 μm or less. It is more preferably 0 μm or less. Among them, the average particle size of both the inorganic substance (1) and the second metal-containing material is preferably 0.9 μm or less (preferably 0.6 μm or less, more preferably 0.5 μm or less).

<Hydrophilic component>
The composition preferably contains a hydrophilic component selected from the group consisting of a hydrophilic binder precursor and a hydrophilic binder.
The content of the hydrophilic component in the composition is not particularly limited, but is preferably 20 to 99.8% by mass, more preferably 20 to 90% by mass, and 40 to 99% based on the total solid content of the composition. Mass% is more preferable.
The hydrophilic components 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.

When a film is formed on a substrate using a composition containing a hydrophilic component, the inorganic substance (1) and the second metal-containing material can be more firmly immobilized on the substrate by the hydrophilic binder.
As a result, for example, even when the film is applied to an application in which the film comes into contact with a liquid, the liquid prevents the inorganic substance (1) and the second metal-containing substance from flowing out of the film. Specifically, even when the above film is formed on a substrate such as a diaper, urine suppresses the outflow of the inorganic substance (1) and the second metal-containing substance to the outside of the film, so that the antibacterial property and The deodorant property can be continuously expressed. In addition, adverse effects on the skin due to the outflow of the inorganic substance (1) and the second metal-containing substance to the outside of the film can be suppressed.

Further, since the hydrophilic binder has hydrophilicity, it has a high affinity with odorants such as ammonia and trimethylamine. Therefore, the hydrophilic binder also has an action of holding and diffusing the odorous substance on the film surface and increasing the chance of contact between the odorous substance and the inorganic substance (1) and the second metal-containing substance. Further, according to the composition containing the hydrophilic component, the excellent deodorizing property is likely to be maintained for a longer time.
The hydrophilic binder precursor means a material capable of forming a hydrophilic binder by a curing reaction such as condensation and polymerization.
The hydrophilic binder means a material capable of forming a hydrophilic film capable of supporting the inorganic material (1) and the second metal-containing material. As the hydrophilic binder, when a film made of the above hydrophilic binder is formed on a glass substrate, for example, the water contact angle is preferably 60 ° or less, and more preferably 50 ° or less. The lower limit of the water contact angle is not particularly limited, but is generally preferably 5 ° or more.
The water contact angle is measured based on the sessile drop method of JIS R 3257: 1999. FAMMS DM-701 manufactured by Kyowa Interface Science Co., Ltd. is used for the measurement.

The hydrophilic component is not particularly limited, but a silicate compound, a monomer having a hydrophilic group (hereinafter, also referred to as “hydrophilic monomer”), and a polymer having a hydrophilic group (hereinafter, referred to as “hydrophilic group”) because they are more excellent in robustness. , Also referred to as a "hydrophilic polymer").
The monomer having a hydrophilic group means a compound having a hydrophilic group and a polymerizable group. The hydrophilic monomer is polymerized to form a hydrophilic polymer when the composition contains a polymerization initiator described below.
The silicate compound, the hydrophilic monomer and the hydrophilic polymer will be described below.

(Silicate compounds)
In the present specification, the silicate compound is a compound selected from the group consisting of a compound in which a hydrolyzable group is bonded to a silicon atom, a hydrolyzate thereof, and a hydrolyzed condensate thereof. At least one selected from the group consisting of the compound represented by 1), a hydrolyzate thereof, and a hydrolytic condensate thereof can be mentioned.
Formula (1) Si- (OR) ₄
In the above formula (1), R represents an alkyl group having 1 to 4 carbon atoms and 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 and tetra-t. -Butyl silicate, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate, etc. are mentioned.

The hydrolyzate of the compound represented by formula (1) means a compound obtained by hydrolyzing the OR group in the compound represented by formula (1). The above-mentioned hydrolyzate is one in which all of the OR groups are hydrolyzed (complete hydrolyzate), but some of the OR groups is hydrolyzed (partial hydrolyzate). You may. That is, the hydrolyzate may be a complete hydrolyzate, a partial hydrolyzate, or a mixture thereof.
Further, the hydrolytic condensate of the compound represented by the formula (1) means a compound obtained by hydrolyzing the OR group in the compound represented by the formula (1) and condensing the obtained hydrolyzate. Intended. As the hydrolysis-condensation product, even if all the OR groups are hydrolyzed and all the hydrolysis products are condensed (complete hydrolysis-condensation product), some of the OR groups are hydrolyzed. It may be decomposed and a part of the hydrolyzate is condensed (partial hydrolyzed condensate). That is, the hydrolysis-condensation product may be a complete hydrolysis-condensation product, a partial hydrolysis-condensation product, or a mixture thereof.
The degree of condensation of the hydrolyzed condensate is preferably 1 to 100, more preferably 1 to 20, and even more preferably 3 to 15.

  The compound represented by the formula (1) is in a state of being at least partially hydrolyzed by being mixed with the water component. The hydrolyzate of the compound represented by the formula (1) is obtained by reacting the compound represented by the formula (1) with a water component to convert the silicon-bonded OR group into a hydroxy group. It is not always necessary for all OR groups to react during hydrolysis, but it is preferable that as many OR groups as possible be hydrolyzed in order to exhibit hydrophilicity after coating. Further, the minimum amount of water component necessary for hydrolysis is the same molar amount as the OR group of the compound represented by the formula (1), but a large excess amount of water is present for the reaction to proceed smoothly. Preferably.

The hydrolysis reaction of the silicate compound proceeds even at room temperature, but may be heated to accelerate the reaction. In addition, a longer reaction time is preferable because the reaction proceeds further. Further, the hydrolyzate can be obtained in about half a day in the presence of a catalyst.
Incidentally, the hydrolysis reaction is generally a reversible reaction, and when water is removed from the system, the hydrolyzate of the silicate compound starts to condense between the hydroxy groups. Therefore, when an aqueous solution of a hydrolyzate is obtained by reacting a large excess of water with the silicate compound, it is preferable to use the aqueous solution as it is without forcibly isolating the hydrolyzate therefrom.

  A preferred form of the silicate-based compound is a compound represented by the formula (X).

Here, in formula (X), R ^{1 to} R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms. Moreover, n represents the integer of 2-100.
3-15 are preferable and, as for n, 5-10 are more preferable.

Examples of commercially available silicate-based compounds include "Ethyl silicate 48" manufactured by Colcoat Co., Ltd., "MKC silicate MS51" manufactured by Mitsubishi Chemical Co., Ltd., and the like.
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, and examples thereof include polyoxyalkylene groups (eg, polyoxyethylene groups, polyoxypropylene groups, polyoxyalkylene groups in which oxyethylene groups and oxypropylene groups are block- or random-bonded), amino groups. , Carboxy group, alkali metal salt of carboxy group, hydroxy group, alkoxy group, amide group, carbamoyl group, sulfonamide group, sulfamoyl group, sulfonic acid group, and alkali metal salt of sulfonic acid group. 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 resulting film is more hydrophilic.

The polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group, a cation polymerizable group, and an anionic polymerizable group. Examples of the radically polymerizable group include (meth) acryloyl group, acrylamide group, vinyl group, styryl group, and allyl group. Examples of cationically polymerizable groups include vinyl ether groups, oxiranyl groups, and oxetanyl groups. Among them, the (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 even more preferably 2 to 3 from the viewpoint that the mechanical strength of the obtained film is more excellent. .

The structure of the main chain of the hydrophilic polymer formed by 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 ones can be used. The definition of the hydrophilic group is as described above.
Examples of the hydrophilic polymer include polymers obtained by polymerizing the above hydrophilic monomers. Other than that, for example, a cellulosic compound may be mentioned. The term “cellulosic compound” means a compound having cellulose as a core, and examples thereof include carboxymethyl cellulose, and nanofibers made of triacetyl cellulose as a raw material.
The weight average molecular weight of the hydrophilic polymer is not particularly limited, but 1,000 to 1,000,000 are preferable, and 10,000 to 500,000 are more preferable, from the viewpoint of better handling properties such as solubility. In addition, in this specification, a weight average molecular weight is defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
The hydrophilic polymers may be used alone or in combination of two or more.

<Solvent>
The composition contains a solvent.
The content of the solvent in the composition is not particularly limited, but the solid content of the composition is preferably adjusted to 0.001 to 80 mass% from the viewpoint that the composition has more excellent coatability. , 0.01 to 10% by mass is more preferable, and 0.1 to 5.0% by mass is more preferable.
The solvent 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.

  The solvent is not particularly limited, and examples thereof include water and / or an organic solvent. Examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenylethyl alcohol, capryl alcohol, lauryl alcohol, and Alcoholic 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 ether solvents such as glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; Aliphatic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether, and di-n-butyl ether; acetone, methyl ethyl ketone, and methyl isobutyl ketone Ketone-based solvent; ester-based solvent such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, ethyl propionate, and butyl propionate A 10% denatonium benzoate alcohol solution, geraniol, octaacetylated sucrose, brucine, linalool, linalyl acetate, and a hydrophilic solvent such as acetic acid; As the solvent, alcohol is preferable, and ethanol or isopropyl alcohol is more preferable, because it is easy to suppress the elution of the metal contained in the inorganic substance (1) and the second metal-containing material into the solvent.

  In the above composition, the content of alcohol is preferably 5% by mass or more with respect to the total mass of the composition, from the viewpoint of suppressing sedimentation of the particulate matter and more excellent in deodorizing property of the formed film. It is preferably 10% by mass or more. The upper limit is not particularly limited, but for example, preferably 99% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 45% by mass or less.

  When the solvent contains alcohol, the content of the alcohol in the solvent is not particularly limited, but is preferably 0.001 to 100% by mass, more preferably 0.01 to 90% by mass with respect to the total mass of the solvent. It is more preferably 5 to 90% by mass, and particularly preferably 5 to 80% by mass.

<Other ingredients>
The above-mentioned composition may contain other components within the range in which the effects of the present invention are exhibited. Other components include, for example, deodorants, antibacterial agents, ultraviolet absorbers, preservatives, pH adjusters, defoamers, polymerization initiators, catalysts, photocatalytic materials, surfactants, fillers, antiaging agents. , Known additives such as antistatic agents, flame retardants, adhesion promoters, leveling agents, matting agents, light stabilizers, dyes, pigments, dispersants, perfumes, film-forming agents, and dispersion stabilizers. ..
Above all, the composition preferably contains a surfactant as a stabilizer.

(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.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
Examples of the polymerization initiator include aromatic ketones such as benzophenone and phenylphosphine oxide; α-hydroxyalkylphenone-based compounds (BASF Corporation, IRGACURE 184, 127, 2959, and DAROCUR 1173); phenylphosphine oxide-based compounds. Compounds (monoacylphosphine oxide: IRGACURE TPO manufactured by BASF, bisacylphosphine oxide: IRGACURE 819 manufactured by BASF); and the like.
Among them, the 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 initiators may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

(Dispersant)
When at least one of the inorganic material (1) and the second metal-containing material is particulate, the composition preferably contains a dispersant.
The dispersant is not particularly limited, and a known dispersant can be used.
As the dispersant, a nonionic or anionic dispersant is preferable. From the viewpoint of affinity with the inorganic substance (1) and the second metal-containing material, a dispersant having an anionic polar group such as a carboxy group, a phosphoric acid group, and a hydroxyl group (an anionic dispersant) is more preferable.
A commercial item can be used as an anionic dispersant. Specific examples thereof include trade names of BYK, DISPERBYK (registered trademark) -110, -111, -116, -140, -161, -162, -163, -164, -170, -171, -174,-. Suitable examples are 180 and -182.

The content of the dispersant in the composition is not particularly limited, but is, for example, 70% by mass or less, and preferably 50% by mass or less, based on the total solid content of the composition. The lower limit is not particularly limited, but is, for example, 0.01% by mass or more, preferably 1.0% by mass or more, and more preferably 15% by mass or more from the viewpoint that the deodorant property of the formed film is more excellent.
The dispersants 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 above composition contains a silicate compound, the composition may contain a catalyst that accelerates the condensation of the silicate compound (hereinafter also referred to as “reaction catalyst”).

The catalyst is not particularly limited, but examples thereof include an alkali catalyst and an organometallic catalyst.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.
As the organometallic catalyst, aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum chelate compound such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate), And zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate), titanium tetrakis (acetylacetonate), and titanium chelate compounds such as titanium bis (butoxy) bis (acetylacetonate), and dibutyltin diacetate, Examples thereof include organic tin compounds such as dibutyltin dilaurate and dibutyltin dioctiate.
Among them, in terms of obtaining a composition having a more excellent effect of the present invention, the catalyst is preferably an organometallic catalyst, and among them, an aluminum chelate compound or a zirconium chelate compound is more preferable, and an aluminum chelate compound is further preferable. preferable.

The content of the catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and still more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the composition. ..
The catalysts may be used alone or in combination of two or more. When two or more catalysts are used in combination, the total content is preferably within the above range.

(Surfactant)
The composition may contain a surfactant. The surfactant has a function of improving the coating property of the composition.
The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
The content of the surfactant is not particularly limited, but is preferably 0.01 part by mass or more based on 100 parts by mass of the total solid content of the composition. The upper limit of the content of the surfactant is not particularly limited, but is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, 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 surfactants may be used alone or in combination of two or more. When two or more kinds are used in combination, the total content thereof is preferably within the above range.

  Examples of the nonionic surfactant 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, alkylbenzene sulfonates, and alkyl phosphates; cationic surfactants such as alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts; alkyl carboxy. An amphoteric surfactant such as betaine can be used.

(Fragrance)
The composition may contain a fragrance.
As flavors, flavors 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, flavors T-100, T-101, T-102, T-103, T-104, T-105, T-106, T-107, EDA-171 manufactured by Takasago International Co., Ltd. Flavor S-201, flavor DA-40 manufactured by Riken Fragrance Co., Ltd., and the like may be included.
The content of the fragrance is preferably 0.01 to 5 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-mentioned silicate compound, hydrophilic monomer, and hydrophilic polymer.
Examples of the film forming agent include thermoplastic resins. The film forming agent functions as a binder when, for example, a film described later is formed.
The thermoplastic resin will be described below.
As the thermoplastic resin, a resin having a minimum film forming temperature of 0 to 35 ° C. is preferable, and a known thermoplastic resin can be used. For example, polyurethane resin, polyester resin, (meth) acrylic resin, polystyrene resin, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether Ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer resin, fluorene ring modified polycarbonate resin, alicyclic modified polycarbonate resin, and fluorene ring modified polyester resin Etc. Among them, (meth) acrylic resin or urethane resin is preferable.
The thermoplastic resins may be used alone or in combination of two or more.
The content of the thermoplastic resin may be appropriately adjusted according to the type of the thermoplastic resin and the like, but for example, 30% by mass or less is preferable, and 20% by mass or less is more preferable, based on the total solid content of the composition. .

(Antibacterial agent and deodorant)
The composition is, for example, a quaternary ammonium salt, a phenol ether derivative, an imidazole derivative, a sulfone derivative, an N-haloalkylthio compound, an anilide derivative, a pyrrole derivative, a pyridine compound, a triazine compound, a benzisothiazoline compound as an antibacterial agent. , And an organic antibacterial agent such as an isothiazoline compound.

  In addition, the composition, as a deodorant, inorganic acids such as phosphoric acid and nitric acid or salts thereof; malic acid, citric acid, and organic acids such as ascorbic acid or salts thereof; dibutylhydroxytoluene; butylhydroxyanisole; hinokitiol. A phenol; a compound containing a phenolic hydroxyl group such as tannic acid, oyster tannin, and tea tannin may be contained.

Examples of the inorganic acid include phosphoric acid, sulfurous acid, sulfuric acid, and alkali metal salts thereof.
Examples of the organic acid include malic acid, citric acid, lactic acid, tartaric acid, salicylic acid, gluconic acid, adipic acid, phytic acid, fumaric acid, succinic acid, ascorbic acid, sorbic acid, glyoxylic acid, melduric acid, glutamic acid, ferulic acid. Examples thereof include acids, picric acid, aspartic acid, and their alkali metal salts. Among organic acids, those having a higher molecular weight tend to be less likely to volatilize, and therefore the pH of the film surface formed using the composition is easily maintained at 6.5 or less.

As the deodorant, malic acid or citric acid is preferable, and malic acid is more preferable, because it is less likely to volatilize and is more excellent in deodorizing property.
When a compound having an antioxidant function (for example, phosphite, ferulic acid, dibutylhydroxytoluene, butylhydroxyanisole, and ascorbic acid) is used as the deodorant, the above-mentioned inorganic substances (1) and The deterioration of the metal-containing component is more easily suppressed, and the antibacterial property and deodorant property of the film are more excellent.
Further, as the deodorant, it is also preferable to use a deodorant having an antioxidant function and a deodorant other than the deodorant having an antioxidant function in combination. When a deodorant having an antioxidant function and a deodorant other than the deodorant having an antioxidant function are used in combination, the antibacterial property and the deodorant property of the film last longer.

<PH of composition>
The pH of the composition is not particularly limited, but it is preferable to adjust the pH to an appropriate range in consideration of rough hands of the user in an actual use environment.
In general, the pH of the composition is preferably 2.0 to 12.0, more preferably 3.0 to 11.0, and further preferably 6.0 to 8.0.
When the composition contains, for example, a component that dissolves in an acid or an alkali or a component that easily deteriorates as the inorganic substance (1) and the second metal-containing material, the composition has a pH within the above range. Has a superior effect of the present invention.
As a method of adjusting the pH of the composition, a method of adding an acid or an alkali to the above composition can be mentioned.
The pH can be measured in a 25 ° C. environment using a commercially available pH meter (for example, pH meter HM-30R manufactured by Toa DKK Co., Ltd.).

<Specific gravity of composition>
The specific gravity of the composition is not particularly limited, but is preferably 0.5 to 1.2.

<Viscosity of composition>
The viscosity of the composition is not particularly limited and may be adjusted according to the application.
For example, when applied to coating properties or spraying, the viscosity of the composition at 25 ° C. is preferably 300 cP (centipoise: 1 cp = 1 mPa · s) or less, more preferably 200 cP or less, still more preferably 0.1 to 150 cP.
When the antibacterial and deodorant effects are maintained for a long time, the viscosity of the composition at 25 ° C. is preferably 250 cP or higher, more preferably 300 cP or higher, even more preferably 400 cP or higher. The upper limit is, for example, 500 cP or less.
The viscosity can be measured using Toki Sangyo Co., Ltd. VISCOMETER TUB-10 or Sekonic SEKONIC VISCOMETER.

<Zeta potential of composition>
The zeta potential of the composition is not particularly limited, but it is preferably adjusted to an appropriate range in view of the fact that the particles are appropriately dispersed in the composition and are excellent in sedimentation resistance. The zeta potential of the composition is preferably 80 mV to -80 mV, more preferably 70 mV to -70 mV, and further preferably 60 mV to -60 mV.
The zeta potential can be measured by a known method, and a predetermined amount of the dispersion liquid is introduced into a glass-made dedicated measuring cell, and can be measured by using ELSZ1EAS manufactured by Otsuka Electronics Co., Ltd.

<Method for producing composition>
In addition, the said composition can contain other additive as needed in the range which produces the effect of this invention.
The composition can be prepared by appropriately mixing the above-mentioned essential components and optional components. The order of mixing the above components is not particularly limited.

<Use of composition>
A film can be formed using the above composition.
The method of forming the film is not particularly limited, but a method of applying the composition to a desired substrate or article to form a coating film and drying or curing the composition to form a film (application method) is preferable.
The method of applying the above composition to a desired substrate or article is not particularly limited. Examples include sprays, roll coaters, gravure coaters, screens, spin coaters, flow coaters, inkjets, electrostatic coating, and wipes. Among them, spraying or wiping is preferable, and wiping is more preferable, because a film can be formed on the surface of an existing article according to demand and treatment (on-demand treatment) can be performed.
The method for forming the film by wiping is not particularly limited, and a known method can be used. For example, the following method may be mentioned. First, a base fabric such as a non-woven fabric is impregnated with the composition, and then the base fabric or the surface of an article is wiped with the base fabric. As a result, a coating film of the above composition is formed on the substrate or the surface of the article. Then, the formed coating film is dried or cured to obtain a film.

  Moreover, according to the said composition, the modified base material excellent in deodorant property and antibacterial property can be formed so that it may mention later. When a modified substrate is obtained using the above composition, the composition may further contain a polymer and a curable compound. The polymer and the curable compound are not particularly limited, and examples thereof include sodium polyacrylate and the like.

〔film〕
The film of the present invention contains an inorganic material (1) and a second metal-containing material.

<Inorganic substance (1)>
The inorganic substance (1) is the same as the inorganic substance (1) contained in the above composition, and the preferable forms are also the same.

<Second metal inclusion>
The second metal-containing material is the same as the second metal-containing material contained in the composition, and the preferred form is also the same.

<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 having a hydrolyzable group bonded to a silicon atom, and a hydrolyzed condensate thereof; a polymer having a hydrophilic group, and the like. At least one selected from the group consisting of a hydrolyzate of a compound having a decomposable group bonded thereto and a hydrolyzed condensate thereof is preferable.
The preferred form of the compound having a hydrolyzable group bonded to the silicon atom and the preferred form of the polymer having a hydrophilic group are as described above.

<Other ingredients>
The membrane may further contain components other than the components described above.

<Membrane manufacturing method>
The film of the present invention is obtained, for example, by drying or curing the above composition. The composition is as described above.
In addition, when the said composition contains a hydrophilic binder precursor as a hydrophilic component, the said film is obtained by hardening the coating film (composition layer) of a composition. In other words, the film is obtained by curing the composition layer to convert the hydrophilic binder precursor in the composition layer into 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 a curing treatment on the composition.

<Film thickness>
The film thickness of the film is not particularly limited, but is preferably 0.001 to 50 μm, more preferably 0.01 to 10 μm.
The film thickness is measured by embedding a sample piece of the film in a resin, shaving the cross section with a microtome, and observing the cut section with a scanning electron microscope. The thickness of any given 10 points on the film is measured, and the arithmetic mean of these values is intended.

<PH of the membrane>
The membrane surface pH of the membrane is typically preferably 7.0 or less, and is particularly preferably 6.5 or less because it is more excellent in deodorizing properties against odorous substances derived from urine and feces such as ammonia and trimethylamine. 0.0 or less is more preferable, and 4.5 or less is further preferable. The lower limit of the film surface pH of the film is not particularly limited, but is preferably 1.0 or more.
In the present specification, the film surface pH of the film is 0.02 mL of liquid droplets (pure water) dropped on the film surface, and after 1 minute has elapsed, the pH of the liquid droplets is measured by the Horiba, Ltd. It is a value obtained by measuring with a meter LAQUA F-72.

  As described below, the membrane can be applied to applications such as diapers. At this time, when the odorant-containing liquid such as urine adheres to the film surface, if the film surface pH is set within the above numerical range (preferably the film surface pH 6.5 or less), the inorganic substance (1 ) And the metal in the second metal-containing material are less likely to deteriorate, and the antibacterial property and deodorant property are more excellent.

An example of a film having a film surface pH in the above numerical range is, for example, a film containing an inorganic substance (1), a second metal-containing substance, and an organic acid. Since the organic acid has low volatility, it exists in a fixed state on the hydrophilic binder in a dry state. When an odorant-containing liquid such as urine adheres to the film surface, the odorant-containing liquid dissolves the organic acid on the film surface, and the film surface pH of the film is likely to fall within the above range. By doing so, the pH of the film surface does not become too low in the state before the odorant-containing liquid adheres, and the metals in the inorganic substance (1) and the second metal-containing substance contained in the film are unlikely to deteriorate.
Further, as another example of the film having a film surface pH within the above numerical range, a film soluble in an odorant-containing liquid, a compound having a pH adjusting function contained in the film, or the like (may be the above-mentioned organic acid) Examples include a method in which the film contains microcapsules having and. When an odorant-containing liquid adheres to the film surface of the film containing the microcapsules, the film of the microcapsules dissolves and the compound having a pH adjusting function is exposed on the film surface, and the film surface pH of the film tends to fall within the above range. .. Further, in this case, the pH of the film surface does not become too low in the state before the odorant-containing liquid adheres, and the metal in the inorganic substance (1) and the second metal-containing substance contained in the film does not easily deteriorate. ..

[Substrate with film]
The substrate with a film according to the embodiment of the present invention includes a substrate and the film. The substrate with a film may be a laminate having a substrate and a film, may have a film on one surface of the substrate, or may have a film on both surfaces of the substrate. You may.

<Substrate>
The base material plays a role of supporting the membrane, and its type is not particularly limited.
The shape of the base material is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, a fiber shape, and a particle shape.
The material forming the base material is not particularly limited, and examples thereof include metal, glass, ceramics, and plastic (resin). Among them, plastic is preferable from the viewpoint of handleability. In other words, the base material is preferably a resin base material.

[Manufacturing method of substrate with film]
The method for producing a film of the present invention corresponds to the method for producing a film using the above-mentioned composition, and has the following steps.
(1) When the composition contains a hydrophilic binder precursor as a hydrophilic component, it has the following step A and the following step B.
(2) When the composition contains a hydrophilic binder as the hydrophilic component, it has the following step A.
(Step A) A step of applying a composition to the surface of a substrate to form a composition layer (Step B) a step of curing the composition layer to obtain a film explain.

(Process A)
Step A is a step of applying a composition to the surface of the base material to form a composition layer. The method of applying the composition to the surface of the base material is not particularly limited, and a known application method can be used.
Examples of the method for applying the composition to the surface of the base material include the methods described above.

The film thickness of the composition layer is not particularly limited, but the dry film thickness is preferably 0.001 to 10 μm.
After applying the composition, a heat treatment may be performed to remove the solvent. The condition of the heat treatment in that case is not particularly limited, and for example, the heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 15 to 600 seconds.
The base material that can be used in step A is the same as the form of the base material described above.

(Process B)
Step B is a step of curing the composition layer to obtain a film. That is, it is a step of converting the hydrophilic binder precursor contained in the composition layer into a hydrophilic binder by a curing reaction such as condensation or polymerization.
The method for curing the composition layer is not particularly limited, and examples thereof include heat treatment and / or exposure treatment.
The exposure treatment is not particularly limited, and examples thereof include a form in which a composition layer is cured by irradiating an ultraviolet ray with an irradiation amount of 100 to 600 mJ / cm ² by an ultraviolet lamp.
In the case of ultraviolet irradiation, ultraviolet rays emitted from light rays such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, and metal halide lamp can be used.
Although the temperature of the heat treatment is not particularly limited, for example, 50 to 150 ° C is preferable, and 80 to 120 ° C is more preferable.

[Modified base material]
The modified substrate of the present invention includes a substrate and a component containing the inorganic substance (1) and the second metal, which is arranged on or in the substrate.
When the modified base material of the present invention has an inorganic substance (1) and a component containing a second metal on the base material, the modified base material of the present invention is disposed on the base material and the above-mentioned base material. It is also preferable to have a composition containing the prepared inorganic substance (1), a component containing a second metal, and a hydrophilic binder.

The shape of the base material is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, and a fiber shape. The term “fibrous” as used herein means a fiber and a structure such as a two-dimensional structure and a three-dimensional structure formed of the fiber (for example, a woven or knitted fabric, and a cloth-like body such as a non-woven fabric).
The material forming the base material is not particularly limited, and examples thereof include natural resins and synthetic resins.

Hereinafter, embodiments of the modified base material will be described.
For example, when the base material is a fiber, examples of the modified base material include a form having a fiber, an inorganic substance (1) attached to the surface of the fiber, and a second metal-containing component.
When the base material is a fibrous structure, the modified base material may include a fibrous structure, an inorganic substance (1) attached to the surface of the fibrous structure, and a second metal-containing component, and a fibrous structure. Examples include a body and an inorganic substance (1) and a second metal-containing component inside the fiber structure. When the base material is a fiber or a fiber structure, the content of the inorganic substance (1) and the second metal-containing component in the modified base material is 0.0001 to 10 mass with respect to the mass of the fiber or fiber structure. % Is preferred.
The method for forming the modified base material in which the base material is a fiber or a fiber structure is not particularly limited, and, for example, after applying the composition described above to the fiber or the fiber structure by a method such as impregnation and spraying, this is Examples include a method of forming a modified substrate by drying. When the composition contains a hydrophilic binder precursor, heat treatment and / or exposure treatment may be performed.
Further, as another example of the method for forming the modified base material that is the fiber structure, for example, a slurry is prepared by mixing a fiber material such as pulp and the composition described above, and wet-type papermaking using the slurry as a raw material. The method includes forming a modified base material having a fiber structure and a component containing the inorganic substance (1) and the second metal arranged in the fiber structure by a method.

  The modified substrate has, for example, a form having a molded body (for example, a sheet-shaped molded body) formed of a resin, the inorganic substance (1) and the second metal-containing component disposed inside the molded body. Good. The resin is not particularly limited, and examples thereof include synthetic resins (water-absorbing polymers such as sodium polyacrylate). The modified base material according to the above embodiment can be formed using the composition described above. As a specific production method, there is a method of casting the above-mentioned composition to form a cast film, and then performing drying, heating, and / or curing. When the modified substrate according to the above embodiment is formed using the composition described above, the composition preferably further contains a polymer, a curable compound, and the like. The polymer and the curable compound are not particularly limited, and examples thereof include sodium polyacrylate and the like.

<Inorganic substance (1)>
The inorganic substance (1) is the same as the inorganic substance (1) contained in the above composition, and the preferable forms are also the same.
<Second metal inclusion>
The second metal-containing material is the same as the second metal-containing material contained in the composition, and the preferred form is also the same.

<Combination of inorganic substance (1) and second metal-containing substance>
The combination of the inorganic substance (1) and the second metal-containing material is also the same as the preferable form of the combination of the inorganic substance (1) and the second metal-containing material in the composition described above.

<Hydrophilic binder>
The modified base material preferably contains a hydrophilic binder. The hydrophilic binder is not particularly limited, and examples thereof include a hydrolyzate of a compound having a hydrolyzable group bonded to a silicon atom, and a hydrolyzed condensate thereof; a polymer having a hydrophilic group, and the like. At least one selected from the group consisting of a hydrolyzate of a compound having a decomposable group bonded thereto and a hydrolyzed condensate thereof is preferable.
The preferred form of the compound having a hydrolyzable group bonded to a silicon atom and the preferred form of the polymer having a hydrophilic group are the same as those described as the hydrophilic component that can be contained in the composition.

<Other ingredients>
The modified base material may further include components other than the components described above.

[Wet wiper]
A wet wiper according to an embodiment of the present invention includes a base cloth and a composition obtained by impregnating the base cloth. The composition is as described above.

The base cloth is not particularly limited, and may be formed of natural fibers or chemical fibers.
Examples of the natural fiber include pulp, cotton, hemp, flax, wool, chrome, cashmere, mohair, and silk.
Examples of the material of the chemical fiber include rayon, polynosic, acetate, triacetate, nylon, polyester, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyalkylene paraoxybenzoate, and polyclar. .
Among these, the hydrophilic base cloth is preferable among these base cloths because it is easily impregnated with the composition. The hydrophilic base cloth is, for example, a base cloth including fibers having a hydrophilic group such as a hydroxyl group, an amino group, a carboxy group, an amide group, and a sulfonyl group. Specific examples of the hydrophilic base cloth include vegetable fiber, cotton, pulp, animal fiber, rayon, nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.
As the base cloth of the wet wiper, non-woven cloth, cloth, towel, gauze, absorbent cotton, etc. may be used, and non-woven cloth is preferable.
The basis weight (mass per unit area) of the base fabric is preferably 100 g / m ² or less. When impregnating the base fabric with the composition, the amount of impregnation is preferably at least 1 time the mass of the base fabric.

〔spray〕
The spray which concerns on embodiment of this invention has a spray container and the composition accommodated in the said spray container. The composition is as described above.
An example of the spray of the present invention is a form in which the above composition and a propellant are filled in a predetermined container. The propellant used is not particularly limited, but examples thereof include liquefied petroleum gas.

[Composition (reference example)]
The inventor of the present invention also has an excellent antibacterial property by using a composition containing a first metal-supporting inorganic carrier, a first metal-supporting organic carrier, and a solvent (hereinafter, also referred to as “composition (reference example)”). It has been found that a film having excellent properties and excellent deodorant properties can be formed.
Here, the first metal is not particularly limited, but silver or copper is more preferable, and copper is particularly preferable.

<First metal-supporting inorganic carrier>
The inorganic carrier of the first metal-supporting inorganic carrier is the same as the inorganic carrier of the first metal-supporting inorganic carrier that can be included in the composition of the embodiment described above, and the preferred form is also the same.

  The inorganic carrier may be crystalline or amorphous (amorphous), but is preferably amorphous and more preferably glass. Examples of the material that can form the glass include silicates, borosilicates, and phosphates. Of these, silicates are preferable, and aluminum silicate is more preferable.

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

  The average particle size of the first metal-supporting inorganic carrier is not particularly limited, but is preferably 4.0 μm or less, more preferably 1.5 μm or less, further preferably 1.0 μm or less, particularly preferably 0.7 μm or less, 0.5 μm The following is most preferable, 0.2 μm or less is the most preferable, and 0.15 μm or less is the most preferable. The lower limit is preferably 0.01 μm or more, more preferably 0.10 μm or more. The method for measuring the average particle size of the first metal-supporting inorganic carrier and the method for adjusting the same are the same as the method for measuring the average particle size of the inorganic substance (1) that can be contained in the composition of the embodiment described above, and the method for adjusting the same. It is the same.

  The aspect ratio of the first metal-supporting inorganic carrier is not particularly limited, but is preferably 1-40, more preferably 2-20. The aspect ratio is calculated by the above method.

  The content of the first metal-supporting inorganic carrier in the composition (reference example) is not particularly limited, but is preferably 0.01 to 40 mass% with respect to the total solid content of the composition, and 0.1 to 30. Mass% is more preferable, and 0.1-10 mass% is still more preferable.

<First metal-supported organic carrier>
The organic carrier of the first metal-supporting organic carrier is not particularly limited, and examples thereof include polymer particles.
Specific examples of the first metal-supported organic carrier include polymer particles supporting copper particles or copper oxide particles (copper-supported polymer).
The copper-supporting polymer is the same as the copper-supporting polymer mentioned as a specific example of the second metal-supporting organic carrier that can be contained in the composition of the embodiment described above.

The average particle diameter of the first metal-supporting organic carrier is not particularly limited, but is generally preferably 0.01 μm or more, more preferably 0.2 μm or more, still more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, more preferably 1.0 μm or less. When considering the sedimentation property of the first metal-supporting organic carrier and the transparency of the composition, the smaller the average particle size of the first metal-supporting organic carrier is, the better the dispersibility is, and as a result, the transparency of the composition is improved. It becomes high and is preferable. In this case, the average particle size of the first metal-supporting organic carrier is preferably 1.0 μm or less, more preferably 0.5 μm or less, still more preferably 0.4 μm or less.
By setting the average particle diameter of the first metal-supporting organic carrier within the above numerical range, in the case where the composition (Reference Example) contains the hydrophilic binder described later, in the film formed using the composition (Reference Example). , It becomes easy to fix the first metal-supporting organic carrier in a state of being exposed from the hydrophilic binder. For this reason, the metal is more easily released from the carrier, and the antibacterial property and deodorant property of the film are further excellent.
The method for measuring the average particle diameter of the first metal-supporting organic carrier is the same as the method for measuring the average particle diameter of the inorganic substance (1) that may be contained in the composition of the embodiment described above.

  The content of the first metal-supporting organic carrier in the composition (reference example) is not particularly limited, but is preferably 0.001 to 50 mass% with respect to the total solid content of the composition, and 0.01 to 40. Mass% is more preferable.

<Solvent>
The type of solvent is not particularly limited, but the same solvent as that described as the solvent that can be contained in the composition of the embodiment described above can be used.

<Hydrophilic binder>
The composition (reference example) may contain a hydrophilic component.
The hydrophilic component is the same as that described as the hydrophilic component that can be contained in the composition of the embodiment described above, and the preferred form is also the same.

<Other ingredients>
The composition (reference example) may contain other components.
The other components are the same as the other components that can be contained in the composition of the embodiment described above, and the preferred forms are also the same.

<Physical properties of composition (reference example)>
As various physical properties of the composition (reference example) (pH of the composition, specific gravity of the composition, viscosity of the composition, and zeta potential of the composition), various physical properties (composition of the composition of the composition of the embodiment described above The pH, the specific gravity of the composition, the viscosity of the composition, and the zeta potential of the composition) are the same as those described above, and the preferred forms are also the same.

<Method for producing composition (reference example) and application>
The production method and use of the composition (reference example) are the same as those described as the production method and use of the composition of the embodiment described above, and the preferred form is also the same.

[Membrane (reference example)]
In addition, the present inventor has found that a film containing a first metal-supporting inorganic carrier and a first metal-supporting organic carrier (hereinafter, also referred to as “film (reference example)”) has excellent antibacterial properties and excellent deodorization. It has been found to have sex.
Here, the first metal is not particularly limited, but silver or copper is more preferable, and copper is particularly preferable.

<First metal-supporting inorganic carrier>
The first metal-supporting inorganic carrier is the same as the first metal-supporting inorganic carrier contained in the composition (reference example) described above, and the preferred form is also the same.

<First metal-supported organic carrier>
The first metal-supporting organic carrier is the same as the first metal-supporting organic carrier contained in the composition (reference example) described above, and the preferred form is also the same.

<Hydrophilic binder>
The film (reference example) preferably contains a hydrophilic binder. The hydrophilic binder is not particularly limited, and examples thereof include a hydrolyzate of a compound having a hydrolyzable group bonded to a silicon atom, and a hydrolyzed condensate thereof; a polymer having a hydrophilic group, and the like. At least one selected from the group consisting of a hydrolyzate of a compound having a decomposable group bonded thereto and a hydrolyzed condensate thereof is preferable.
The preferred form of the compound having a hydrolyzable group bonded to the silicon atom and the preferred form of the polymer having a hydrophilic group are the same as those of the composition of the embodiment described above.

<Other ingredients>
The film (reference example) may further contain components other than the components described above.

<Membrane (Reference Example) Manufacturing Method>
The film of the present invention is obtained, for example, by drying or curing the above composition (Reference Example). The composition (reference example) is as described above.
In addition, when the said composition (reference example) contains a hydrophilic binder precursor as a hydrophilic component, the said film (reference example) hardens the coating film (composition layer) of a composition (reference example). can get. In other words, the above-mentioned film (reference example) is obtained by curing the above-mentioned composition layer and using the hydrophilic binder precursor in the composition layer as a hydrophilic binder.
On the other hand, when the hydrophilic component in the composition (reference example) is a hydrophilic binder, it is not necessary to perform a curing treatment on the composition (reference example).

<Thickness of film (reference example)>
The film thickness of the film (reference example) is not particularly limited, but is preferably 0.001 to 50 μm, more preferably 0.01 to 10 μm.
The film thickness is measured by embedding a sample piece of the film in a resin, shaving the cross section with a microtome, and observing the cut section with a scanning electron microscope. The thickness of any given 10 points on the film is measured, and the arithmetic mean of these values is intended.

<PH of membrane (reference example)>
The film surface pH of the film (reference example) is typically preferably 7.0 or less, and particularly 6.5 or less in that it is more excellent in deodorizing property against odorous substances derived from urine and feces such as ammonia and trimethylamine. Is preferred, 5.0 or less is more preferred, and 4.5 or less is even more preferred. The lower limit of the film surface pH of the film (reference example) is not particularly limited, but is preferably 1.0 or more.
In the present specification, the film surface pH of the film (reference example) is 0.02 mL of liquid droplets (pure water) dropped on the film surface, and after 1 minute, the pH of the liquid droplets is measured by Horiba Seisakusho. It is a value when it asks by measuring using pH meter LAQUA F-72 by a company.

  As described later, the film (reference example) can be applied to applications such as diapers. At this time, when the liquid containing an odorous substance such as urine adheres to the film surface, if the film surface pH is set within the above numerical range (preferably the film surface pH is 6.5 or less), it is contained in the film (reference example). The metal in the first metal-supporting inorganic carrier and the first metal-supporting organic carrier is less likely to be deteriorated, and the antibacterial property and deodorant property are more excellent.

An example of a film having a film surface pH in the above numerical range is, for example, a film containing a first metal-supporting inorganic carrier, a first metal-supporting organic carrier, and an organic acid. Since the organic acid has low volatility, it exists in a fixed state on the hydrophilic binder in a dry state. When an odorant-containing liquid such as urine adheres to the film surface, the odorant-containing liquid dissolves the organic acid on the film surface, and the film surface pH of the film is likely to fall within the above range. By doing so, the pH of the film surface does not become too low in the state before the odorant-containing liquid adheres, and the metal in the first metal-supporting inorganic carrier and the first metal-supporting organic carrier contained in the film is altered. Hateful.
Further, as another example of the film having a film surface pH within the above numerical range, a film soluble in an odorant-containing liquid, a compound having a pH adjusting function contained in the film, or the like (may be the above-mentioned organic acid) Examples include a method in which the film contains microcapsules having and. When an odorant-containing liquid adheres to the film surface of the film containing the microcapsules, the film of the microcapsules dissolves and the compound having a pH adjusting function is exposed on the film surface, and the film surface pH of the film tends to fall within the above range. .. Further, in this case, in the state before the odorant-containing liquid is attached, the film surface pH does not become too low, and the metal contained in the film is not contained in the first metal-supporting inorganic carrier and the first metal-supporting organic carrier. Hard to change.

[Substrate with film (reference example)]
The base material with a film (reference example) has a base material and the above-mentioned film (reference example). The film-coated substrate (reference example) may be a laminate having a substrate and a film (reference example), and may have the film (reference example) on one surface of the substrate. A film (reference example) may be provided on both surfaces of the base material.

<Substrate>
The base material plays a role of supporting the film (reference example), and its type is not particularly limited.
The base material is the same as the base material used in the base material with a film of the embodiment described above.

[Manufacturing method of base material with film (reference example)]
The method for producing a film-coated substrate (reference example) corresponds to the method for producing a film (reference example) using the composition (reference example) described above, and has the following steps.
(1) When the composition (reference example) contains a hydrophilic binder precursor as a hydrophilic component, it has the following step A and the following step B.
(2) When the composition (reference example) contains a hydrophilic binder as a hydrophilic component, it has the following step A.
(Step A) A step of applying a composition (reference example) to the surface of a substrate to form a composition layer (step B) a step of curing the composition layer to obtain a film (reference example) The specific procedure of the method for manufacturing a film-coated substrate (reference example) is the same as the procedure of the method for manufacturing a film-coated substrate according to the above-described embodiment.

[Wet wiper (reference example)]
The wet wiper (reference example) has a base fabric and a composition (reference example) impregnated into the base fabric. The composition (reference example) is as described above.
The specific configuration of the wet wiper (reference example) is the same as the specific configuration of the wet wiper according to the embodiment described above, except that the composition used is different.

[Spray (reference example)]
The spray (reference example) includes a spray container and a composition (reference example) housed in the spray container. The composition (reference example) is as described above.
The specific structure of the spray (reference example) is the same as the specific structure of the spray according to the embodiment described above, except that the composition used is different.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following examples.

[Example 1: Preparation of composition 1]
While stirring 367 g of ethanol in a container, 60 g of pure water, 14 g of a silicate compound (“MKC (registered trademark) silicate” MS51 ”manufactured by Mitsubishi Chemical Corporation), aluminum chelate D (aluminum bis (ethylacetoacetate) mono (acetylacetoacetate Nate), ethanol dilution: solid content concentration 1% by mass) 15 g, nonionic surfactant (“Emarex 715” manufactured by Nippon Emulsion Co., Ltd., pure water dilution: solid content concentration 0.5% by mass) 60 g, and anionic interface After 10 g of an activator (sodium di (2-ethylhexyl) sulfosuccinate, diluted with pure water: solid content concentration of 0.2% by mass) was sequentially added, 18 g of isopropanol and a dispersant (“DISPERBYK (registered trademark) -180 manufactured by BYK”). )) 3.6 g, 2.4 g of silver-supported glass particles (manufactured by Fuji Chemical Co., diluted with ethanol: solid content concentration 60% by mass) whose average particle size is adjusted to 0.3 μm, and stirred for 20 minutes to prepare dispersion A. Got
The silver-supported glass particles in this dispersion A correspond to the inorganic substance (1).

In the obtained dispersion liquid A, copper-supported glass (corresponding to “NS-20C” manufactured by Toagosei (inorganic substance (2) as a second metal-containing material. Incidentally, the inorganic carrier of “NS-20C” manufactured by Toagosei is This corresponds to aluminum silicate))) 0.28 g was added and stirred to obtain a composition 1.
The obtained composition 1 of Example 1 contains an inorganic material (1), a second metal-containing material (inorganic material (2)), a silicate compound as a hydrophilic component, and a solvent.

(Average Particle Size of Inorganic Substance (1) and Second Metal Containing Material)
When the inorganic substance (1) and the second metal-containing substance are particles, the average particle size of the particles was measured by observation using an electron microscope. The specific measurement method is as described above.

<Evaluation A>
(Preparation of test sample)
The composition 1 obtained above was evaluated for its deodorant property based on the tests described below.
First, a non-woven fabric was prepared, and the composition 1 was sprayed onto the non-woven fabric so that 1 g of the composition 1 adhered to 100 cm ² of the non-woven fabric. Next, the obtained non-woven fabric with the composition 1 was dried at 25 ° C. for 2 days to prepare the film-coated substrate 1.

(Evaluation of deodorant property)
Urine with an ammonia odor was sprayed onto the film-coated substrate 1 in an amount of 10 g and left at room temperature. After left for 1 hour and after 8 hours, the odor was sensory evaluated. The results are shown in Table 1.

<< Evaluation criteria >>
"A": Almost no odor is felt.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": An odor is felt.
"E": A strong odor is felt.

(Evaluation of antibacterial property)
The antibacterial property of the film-coated substrate 1 was evaluated.
The antibacterial property was evaluated in accordance with the evaluation method described in JIS Z 2801: 2012, and Escherichia coli was used, and the test was carried out by changing the contact time with the bacterial solution to 24 hours. The antibacterial activity value after the test was measured and evaluated based on the following evaluation criteria. The results are shown in Table 1.
<< Evaluation criteria >>
"A": Antibacterial activity value is 2.5 or more "B": Antibacterial activity value is 1.0 or more and less than 2.5 "C": Antibacterial activity value is less than 1.0

(Membrane surface pH)
The antibacterial property of the film-coated substrate 1 was evaluated. The evaluation method is as described above.

[Comparative Example 1: Preparation of composition R1]
Comparative example was carried out in the same manner as in Example 1 except that the second metal-containing material was not used, and the average particle size of the inorganic material (1) was adjusted to the size (μm) shown in Table 1. Composition R1 of No. 1 was prepared.
Various evaluations were performed using the obtained composition R1 in the same manner as in the composition 1. The results are shown in Table 1.

[Example 2: Preparation of composition 2]
Composition 2 was prepared and evaluated in the same manner as in Example 1 except that the average particle sizes of the inorganic material (1) and the second metal-containing material were adjusted to the sizes shown in Table 1. The results are shown in Table 1.

[Example 3: Preparation of composition 3]
Composition 3 was prepared and evaluated in the same manner as in Example 2 except that MKC silicate MS51 was not used. The results are shown in Table 1.

[Comparative Example 2: Preparation of composition R2]
Composition R2 was prepared and evaluated in the same manner as in Comparative Example 1 except that MKC silicate MS51 was not used. The results are shown in Table 1.

[Comparative Example 3: Preparation of composition R3]
Composition R3 was prepared and evaluated in the same manner as in Example 3 except that the silver-supported glass was not used. The results are shown in Table 1.

Table 1 is shown below.
The "copper-supported glass" in Table 1 is "NS-20C" manufactured by Toagosei Co., Ltd., whose average particle size is controlled to the size described in the table. The inorganic carrier of "NS-20C" manufactured by Toagosei corresponds to aluminum silicate.

  From the above results, it was found that the compositions of Examples 1 to 4 containing the inorganic substance (1), the second metal-containing substance, and the solvent had the effects of the present invention. On the other hand, the composition of Comparative Example 1 or 2 containing no second metal-containing material and the composition of Comparative Example 3 containing no inorganic material (1) did not have the effect of the present invention.

  In addition, it was found that the composition of Example 2 containing the hydrophilic component maintained a superior deodorant property even after 8 hours, as compared with the composition of Example 3. It was

[Example 4: Preparation of composition 4]
Composition 4 was prepared in the same manner as in Example 1 except that the average particle size of the inorganic material (1) and the average particle size and aspect ratio of the second metal-containing material were adjusted to the values shown in Table 2. Prepared.
The composition 4 thus prepared was used for evaluation of <Evaluation B> described later, and the results are shown in Table 2. In addition, <Evaluation B> described later is a stricter evaluation condition than <Evaluation A> described later.

<Evaluation B>
(Preparation of test sample)
The composition 4 obtained above was evaluated for its deodorizing property based on the following test.
First, a nonwoven fabric was prepared, and the composition 4 was sprayed onto the nonwoven fabric so that 0.1 g of the composition 4 adhered to 100 cm ² of the nonwoven fabric. Next, the obtained non-woven fabric with the composition 4 was dried at 25 ° C. for 2 days to prepare a film-coated substrate 4.

(Evaluation of deodorant property)
Urine with an ammonia odor was sprayed on the film-coated substrate 4 in an amount of 10 g and left at room temperature. After left for 1 hour and after 8 hours, the odor was sensory evaluated. The results are shown in Table 1.

<< Evaluation criteria >>
"AA": Only a very slight odor is felt.
"A": Almost no odor is felt.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": An odor is felt.
"E": A strong odor is felt.

(Evaluation of antibacterial property)
The antibacterial property of the film-coated substrate 4 was evaluated.
The antibacterial property was evaluated in accordance with the evaluation method described in JIS Z 2801: 2012, and Escherichia coli was used, and the test was carried out by changing the contact time with the bacterial solution to 24 hours. The antibacterial activity value after the test was measured and evaluated based on the following evaluation criteria. The results are shown in Table 2.
<< Evaluation criteria >>
"A": Antibacterial activity value is 2.5 or more "B": Antibacterial activity value is 1.0 or more and less than 2.5 "C": Antibacterial activity value is less than 1.0

(Membrane surface pH)
The antibacterial property of the film-coated substrate 4 was evaluated. The evaluation method is as described above.

[Example 5: Preparation of composition 5]
Composition 5 was prepared and evaluated in the same manner as in Example 4 except that the average particle size and aspect ratio of the second metal-containing material were adjusted to the values described in Table 2. The results are shown in Table 2.

[Example 6: Preparation of composition 6]
Composition 6 was prepared and evaluated in the same manner as in Example 4 except that the average particle size and aspect ratio of the second metal-containing material were adjusted to the values shown in Table 2. The results are shown in Table 2.

[Example 7: Preparation of composition 7]
Composition 7 was prepared in the same manner as in Example 4 except that the average particle size of the inorganic material (1) and the average particle size and aspect ratio of the second metal-containing material were adjusted to the values shown in Table 2. Prepared and evaluated. The results are shown in Table 2.

  Table 2 also shows the results of carrying out the above-mentioned evaluation B using the above-mentioned composition 1 and composition 2.

  The "copper-supported glass" in Table 2 is "NS-20C" manufactured by Toagosei Co., Ltd. in which the average particle size is controlled to the size described in the table. The inorganic carrier of "NS-20C" manufactured by Toagosei corresponds to aluminum silicate glass.

  From the above results, the case where the second metal-containing material is particles and the average particle diameter is 1.5 μm or less (preferably 0.5 μm or less, more preferably 0.2 μm or less, further preferably 0.15 μm or less) It was confirmed that the deodorizing property was further improved.

[Example 8: Preparation of composition 8]
Water was removed by drying the copper oxide particles (“Copper (II) oxide copper OXIDE” manufactured by Kanto Chemical Co., Ltd.) under reduced pressure at a low temperature of 4 ° C. for 40 hours. Next, the dried copper oxide particles were dispersed by diluting with water 10 times, and then wet-milled using a bead mill. The obtained dispersion liquid was dried under reduced pressure at 50 ° C. for 5 hours to prepare CuO powder having an average particle size of 30 nm.
Regarding the copper (II) oxide particles used in the composition 16 (Example 16) described later, the same method as the copper (II) oxide used in the composition 8 except that the milling time and the filter type were changed. The particle size was controlled by.

In a container, 150 g of polymer particles (“Eposter 100W” manufactured by Nippon Shokubai Co., Ltd., average particle size: 150 nm) aqueous dispersion (solid content concentration 0.1% by mass) were stirred, while a silicate compound (“MKC manufactured by Mitsubishi Chemical Corporation” (Registered trademark) Silicate MS51 ") (0.1 g) was added and the mixture was stirred for 20 minutes. Next, 50 g of a particle size-controlled copper oxide (“Copper (II) COPER OXIDE” manufactured by Kanto Chemical Co., Inc.) aqueous dispersion (solid content concentration 0.01% by mass: average particle size 30 nm) was added to the stirred product, The mixture was stirred for another 20 minutes to obtain dispersion C.
The dispersion C contains copper-supporting polymer particles (corresponding to an organic substance containing the second metal) as the second metal-containing substance.

Incidentally, in the present Example section, in the copper-supported polymer particles, for the average particle diameter of the copper oxide particles and the polymer particles, using the dispersion liquid of only the copper oxide particles and the dispersion liquid of the polymer particles, the following dynamic The average particle size obtained by measurement by light scattering was used as a substitute.
(Measurement of average particle size of copper oxide particles and polymer particles)
The average particle size of the copper oxide particles and the polymer particles in the dispersion was measured by dynamic light scattering using a particle size distribution measuring device using laser diffraction.
Specifically, it was measured using a dynamic light scattering measuring device (Zetasizer ZS) manufactured by Marveln. The average particle size was measured three times as a mean value (Z-Average) of the particle size by cumulant analysis according to the method defined by ISO13321, and the average value of the values measured three times was used.

Next, the resulting dispersion C was centrifuged to precipitate the copper-supported polymer particles. The copper-supported polymer particles were separated by filtration and naturally dried under reduced pressure to obtain copper-supported polymer particles. As observed by an optical microscope, the copper-supported polymer particles have a structure in which copper oxide particles are supported on the surface of the polymer particles, and at least one region on the surface of the polymer particles is a silane compound condensed. It was confirmed that a film of the compound was formed.
The copper-supported polymer particles had an average particle size of 0.6 μm.

Composition 8 was obtained by adding 0.1 g of zirconium phosphate having an average particle size controlled to 0.3 μm to the obtained dispersion C as an inorganic substance (1) and stirring the mixture.
The zirconium phosphate corresponds to "NS-10" manufactured by Toagosei Co., Ltd., whose average particle size is controlled to 0.3 µm.
The obtained composition 8 of Example 8 contains an inorganic material (1), a second metal-containing material (organic material containing a second metal), a silicate compound as a hydrophilic component, and a solvent.

<Evaluation C>
(Preparation of test sample)
The composition 8 obtained above was evaluated for its deodorant property based on the tests described below.
First, a non-woven fabric was prepared, and the composition 8 was sprayed onto the non-woven fabric so that 1 g of the composition 8 adhered to 100 cm ² . Next, the obtained non-woven fabric with the composition 8 was dried at 25 ° C. for 2 days to prepare the substrate 8 with a film.

(Evaluation of deodorant property)
10 g of urine having an ammonia odor was sprayed onto the film-coated substrate 8 and left at room temperature. After left for 1 hour and after 8 hours, the odor was sensory evaluated. The results are shown in Table 3.

<< Evaluation criteria >>
"AA": Only a slight odor is felt.
"A": Almost no odor is felt.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": An odor is felt.
"E": A strong odor is felt.

(Evaluation of antibacterial property)
The antibacterial property of the film-coated substrate 8 was evaluated.
The antibacterial property was evaluated in accordance with the evaluation method described in JIS Z 2801: 2012, and Escherichia coli was used, and the test was carried out by changing the contact time with the bacterial solution to 24 hours. The antibacterial activity value after the test was measured and evaluated based on the following evaluation criteria. The results are shown in Table 3.
<< Evaluation criteria >>
"A": Antibacterial activity value is 2.5 or more "B": Antibacterial activity value is 1.0 or more and less than 2.5 "C": Antibacterial activity value is less than 1.0

(Membrane surface pH)
The antibacterial property of the film-coated substrate 8 was evaluated. The evaluation method is as described above.

[Examples 9 to 10: Preparation of compositions 9 to 10]
Compositions 9-10 of Examples 9-10 were prepared in the same manner as composition 8 of Example 8 except that the type and average particle size of the inorganic material (1) were changed to the compositions shown in Table 3. did.
The obtained compositions 9 to 10 of Examples 9 to 10 include an inorganic material (1), a second metal-containing material (organic material containing a second metal), a silicate compound as a hydrophilic component, and a solvent.
Using the compositions 9 to 10 thus obtained, various evaluations were carried out in the same manner as the composition 8. The results are shown in Table 3.

[Examples 16 and 20: Preparation of compositions 16 and 20]
Compositions 16 and 20 of Examples 16 and 20 were prepared in the same manner as composition 8 of Example 8 except that the additives were added in the amounts shown in Table 3.
The obtained compositions 16 and 20 of Example 16 and Example 20 were an inorganic substance (1), a second metal-containing substance (an organic substance containing a second metal), a silicate compound as a hydrophilic component, and Including solvent.
Various evaluations were performed using the obtained composition 16 and composition 20 in the same manner as the composition 8. The results are shown in Table 3.

[Example 11: Preparation of composition 11]
While stirring 367 g of ethanol in a container, 60 g of pure water, 14 g of a silicate compound (“MKC (registered trademark) silicate” MS51 ”manufactured by Mitsubishi Chemical Corporation), aluminum chelate D (aluminum bis (ethylacetoacetate) mono (acetylacetoacetate) Nate), ethanol dilution: solid content concentration 1% by mass) 15 g, nonionic surfactant (“Emarex 715” manufactured by Nippon Emulsion Co., Ltd., pure water dilution: solid content concentration 0.5% by mass) 60 g, and anionic interface After 10 g of an activator (sodium di (2-ethylhexyl) sulfosuccinate, diluted with pure water: solid content concentration of 0.2% by mass) was sequentially added, 18 g of isopropanol and a dispersant (“DISPERBYK (registered trademark) -180 manufactured by BYK”). )) 3.6 g, 2.4 g of silver-supported glass particles (manufactured by Fuji Chemical Co., Ltd., diluted with ethanol: solid content concentration 60% by mass) whose average particle size is controlled to 0.6 μm, and stirred for 20 minutes to prepare dispersion D. Got
The silver-supported glass particles in this dispersion D correspond to the inorganic substance (1).

To the obtained dispersion liquid D, 0.28 g of zirconium phosphate (corresponding to the inorganic material (2)) having an average particle diameter controlled to 0.3 μm was added as a second metal-containing material, and the mixture was stirred to form a composition. Item 11 was obtained.
The zirconium phosphate corresponds to "NS-10" manufactured by Toagosei Co., Ltd., whose average particle size is controlled to 0.3 µm.
The obtained composition 11 of Example 11 contains an inorganic material (1), a second metal-containing material (inorganic material (2)), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed using the obtained composition 11 by the same method as the composition 8. The results are shown in Table 3.

[Examples 12 to 13: Preparation of compositions 12 to 13]
Compositions 12 to 13 of Examples 12 to 13 were prepared in the same manner as composition 11 of Example 11 except that the type and average particle size of the second metal-containing material were changed to those shown in Table 3. Prepared.
The obtained compositions 12 to 13 of Examples 12 to 13 include the inorganic material (1), the second metal-containing material (inorganic material (2)), a silicate compound as a hydrophilic component, and a solvent.
Using the compositions 12 to 13 thus obtained, various evaluations were carried out in the same manner as the composition 8. The results are shown in Table 3.

[Example 14: Preparation of composition 14]
Dispersion C1 was obtained in the same manner as Dispersion C except that the average particle size of the copper-supported polymer particles was changed from 0.6 μm to 0.3 μm.
Composition 14 of Example 14 was prepared in the same manner as composition 8 of Example 8 except that dispersion C1 was used instead of dispersion C1.
The obtained composition 14 of Example 14 contains an inorganic substance (1), a second metal-containing substance (organic substance containing a second metal), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed using the obtained composition 14 in the same manner as in the composition 8. The results are shown in Table 3.

[Example 15: Preparation of composition 15]
Dispersion D1 was obtained in the same manner as Dispersion D, except that the average particle size of the inorganic material (1) (silver-supporting glass) was changed from 0.6 μm to 0.3 μm.
Composition 15 of Example 15 was prepared in the same manner as composition 11 of Example 11 except that Dispersion D was changed to Dispersion D1.
The composition 15 thus obtained contains the inorganic material (1), the second metal-containing material (inorganic material (2)), the silicate compound as a hydrophilic component, and the solvent.
Various evaluations were performed using the obtained composition 15 in the same manner as in the composition 8. The results are shown in Table 3.

[Examples 17, 18, 21: Preparation of Compositions 17, 18, 21]
Further, the compositions 17 and 18 of Examples 17, 18 and 21 were prepared in the same manner as the composition 15 of Example 15 except that the additives were added in the amounts shown in Table 3. And Composition 23 were prepared respectively.
The obtained compositions 17, 18, and 21 of Examples 17, 18, and 21 include the inorganic material (1), the second metal-containing material (inorganic material (2)), the silicate compound as a hydrophilic component, and the solvent.
Using the obtained compositions 17, 18, and 21, various evaluations were carried out in the same manner as the composition 8. The results are shown in Table 3.

[Example 19: Preparation of composition 19]
As the second metal-containing material, a copper-supported glass having an average particle size controlled to the size shown in Table 3 (“NS-20C” manufactured by Toagosei: Inorganic carrier of “NS-20C” manufactured by Toagosei is silicic acid). Dispersion C2 was prepared by the same method except that 0.1 g was added.
The dispersion C2 contains copper-supporting glass (corresponding to the inorganic material (2)) and copper-supporting polymer particles (corresponding to the organic material containing the second metal) as the second metal-containing material. To do.
To the resulting dispersion C, 0.28 g of zirconium phosphate having an average particle size controlled to 0.3 μm was added as an inorganic substance (1) and stirred to obtain a composition 21. The obtained composition 19 of Example 19 contains an inorganic material (1), a second metal-containing material (inorganic material (2), an organic material containing a second metal), a silicate compound, and a solvent.
Various evaluations were performed using the obtained composition 19 in the same manner as in the composition 8. The results are shown in Table 3.

[Example 22: Preparation of composition 22]
In the obtained dispersion liquid D1, 0.28 g of zirconium phosphate having an average particle size controlled to 0.3 μm and a copper-supported glass having an average particle size controlled to the size described in the table ( Toagosei "NS-20C": The inorganic carrier of Toagosei "NS-20C" corresponds to aluminum silicate glass.) 0.1 g was added and stirred to obtain a composition 22. The composition 22 of the obtained Example 22 contains an inorganic material (1), a second metal-containing material (two kinds of the inorganic material (2)), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed using the obtained composition 22 by the same method as the composition 8. The results are shown in Table 3.

[Example 23: Preparation of composition 23]
In the obtained dispersion D1, 0.28 g of zirconium phosphate having an average particle size controlled to 1.1 μm as a second metal-containing material, and copper-supported glass having an average particle size controlled to the size described in the table ( Toa Gosei "NS-20C": The inorganic carrier of "Toagosei" NS-20C "corresponds to aluminum silicate glass.) 0.28 g was added and stirred to obtain a composition 23. The composition 23 obtained in Example 23 contains an inorganic material (1), a second metal-containing material (two kinds of the inorganic material (2)), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed using the obtained composition 23 by the same method as the composition 8. The results are shown in Table 3.

[Comparative Example 4: Preparation of composition R4]
A composition R4 of Comparative Example 4 was prepared in the same manner as in Example 8 except that the inorganic substance (1) was not used.
Using the composition R4 thus obtained, various evaluations were carried out in the same manner as in the composition 8. The results are shown in Table 3.

[Comparative Example 5: Preparation of composition R5]
A composition R5 of Comparative Example 5 was prepared in the same manner as in Example 11 except that the second metal-containing material was not used.
Using the composition R5 thus obtained, various evaluations were carried out in the same manner as in the composition 8. The results are shown in Table 3.

[Comparative Example 6: Preparation of composition R6]
The same as Example 8 except that the dispersant C was not used, and 0.1 g of a silicate-based compound (“MKC (registered trademark) silicate” MS51 ”manufactured by Mitsubishi Chemical Corporation) and 200 g of pure water were used instead of the dispersant C. A composition R6 of Comparative Example 6 was prepared by the method described in 1.
Using the obtained composition R6, various evaluations were carried out in the same manner as in the composition 8. The results are shown in Table 3.

[Comparative Example 7: Preparation of composition R7]
The same method as in Example 11 except that the dispersant D was not used, and 14 g of a silicate-based compound (“MKC (registered trademark) silicate” MS51 ”manufactured by Mitsubishi Chemical Corporation) and 536 g of pure water were used instead of the dispersant D. By this, a composition R7 of Comparative Example 7 was prepared.
Various evaluations were performed by using the obtained composition R7 in the same manner as in the composition 8. The results are shown in Table 3.

"BHT" in the table is an abbreviation for dibutylhydroxytoluene.
"Zirconium phosphate" in the table is "NS-10" manufactured by Toagosei Co., Ltd., whose average particle size is controlled to the size described in the table.
"Phosphate glass" in the table is manufactured by Fuji Chemical Co., Ltd. whose average particle size is controlled to the size described in the table.
The "copper-supported glass" in the table is "NS-20C manufactured by Toagosei: whose average particle size is controlled to the size described in the table: The inorganic carrier of" NS-20C "manufactured by Toagosei is aluminum silicate glass. Applicable It is.

From the results in Table 3, it was confirmed that the films obtained from the compositions of Examples 8 to 23 had excellent antibacterial properties and deodorant properties. In particular, it was confirmed that the deodorant property lasts for a long period of time.
Further, from the comparison with Examples 8 to 14, both the inorganic substance (1) and the second metal-containing substance are particles, and the average particle size of the inorganic substance (1) and the second metal-containing substance are both 0. It was confirmed that when the thickness was 6 μm or less (preferably 0.5 μm or less), the deodorizing property was more excellent.
Further, from the comparison between Example 8 and Example 16 and Example 20, and Example 15 and Example 17 and Example 21, it was confirmed that when citric acid was used together as an additive, the deodorizing property was superior.
Further, from the comparison between Example 8 and Example 19, when two or more metal-supporting carriers are used in combination as the second metal-containing material (preferably, the second metal organic carrier and the second metal inorganic carrier are used in combination). It was confirmed that the deodorizing property was superior.
From the comparison between Example 15 and Example 22, it was confirmed that when the inorganic substance (1) contained silver-supported glass and the second metal-containing substance contained copper-supported glass, the deodorizing property was superior.

[Example 24: Preparation of composition 24]
While stirring 52 g of ethanol in a container, 38 g of pure water, 0.41 g of a silicate-based compound (“MKC (registered trademark) silicate” MS51 ”manufactured by Mitsubishi Chemical Corporation), aluminum chelate D (aluminum bis (ethylacetoacetate) mono ( Acetylacetonate), diluted with ethanol: solid content concentration 1% by mass) 1.3 g, nonionic surfactant (“Emarex 715” manufactured by Nippon Emulsion Co., Ltd., diluted with pure water: solid content concentration 0.5% by mass) 3. 3 g and 0.8 g of an anionic surfactant (“Ravisol A-90” manufactured by NOF CORPORATION, diluted with pure water: solid content concentration 0.2% by mass) were sequentially added, and then 2.7 g of isopropanol and an inorganic substance (1 ) (Silver-supporting glass having an average particle size controlled to 1.1 μm (corresponding to “Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd. having an average particle size controlled to 1.1 μm. The inorganic carrier of "Bacterite MP-103DV" corresponds to phosphate glass.), Ethanol / water solvent dilution: solid content concentration 25.3% by mass) 0.039 g, dispersant ("DISPERBYK (registered trademark) manufactured by BYK Co., Ltd." ) -180 ") 0.04 g, ethanol 1.4 g, second metal-containing material (copper-supported glass having an average particle size controlled to 3.1 [mu] m (Toagosei" NS-20C "has an average particle size of 3.1 [mu] m. Inorganic carrier of "NS-20C" manufactured by Toagosei Co., Ltd. corresponds to aluminum silicate glass.): Solid content concentration 100% by mass) 0.489 g, and stirred for 20 minutes, Composition 24 was obtained.
The composition 24 obtained in Example 24 contains an inorganic material (1), a second metal-containing material (inorganic material (2)), a silicate compound as a hydrophilic component, and a solvent.
Using the obtained composition 24, various evaluations were performed according to the following <Evaluation D>.
In addition, the following evaluation D is a stricter evaluation condition than the above-described evaluations A to C.

<Evaluation D>
(Preparation of test sample)
The composition 24 obtained above was evaluated for its deodorant property based on the tests described below.
First, a non-woven fabric was prepared, and the composition 24 was sprayed onto the non-woven fabric so that 0.06 g of the composition 24 adhered to 100 cm ² of the non-woven fabric. Next, the obtained non-woven fabric with the composition 24 was dried at 25 ° C. for 2 days to prepare a film-coated substrate 24.

(Evaluation of deodorant property)
Urine with an ammonia odor was sprayed on the film-coated substrate 24 in an amount of 10 g and left at room temperature. After left for 1 hour and after 8 hours, the odor was sensory evaluated. The results are shown in Table 4.

<< Evaluation criteria >>
"AA": Only a slight odor is felt.
"A": Almost no odor is felt.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": An odor is felt.

(Evaluation of antibacterial property)
The antibacterial property of the film-coated substrate 24 was evaluated.
The antibacterial property was evaluated in accordance with the evaluation method described in JIS Z 2801: 2012, and Escherichia coli was used, and the test was carried out by changing the contact time with the bacterial solution to 24 hours. The antibacterial activity value after the test was measured and evaluated based on the following evaluation criteria. The results are shown in Table 4.
<< Evaluation criteria >>
"A": Antibacterial activity value is 2.5 or more "B": Antibacterial activity value is 1.0 or more and less than 2.5 "C": Antibacterial activity value is less than 1.0

[Examples 25 to 30: Preparation of compositions 25 to 30]
Compositions 25 to 30 were prepared and evaluated in the same manner as in Example 24, except that the contents of the inorganic substance (1) and the second metal-containing substance were adjusted to the amounts shown in Table 4. The results are shown in Table 4.

[Examples 31 to 37: Preparation of compositions 31 to 37]
Compositions 31 to 37 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle size of the inorganic material (1) was adjusted to the size shown in Table 4. The results are shown in Table 4.

Examples 38-44: Preparation of Compositions 38-44
Compositions 38 to 44 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle size of the inorganic material (1) was adjusted to the size shown in Table 4. The results are shown in Table 4.

[Examples 45 to 51: Preparation of compositions 45 to 51]
Compositions 45 to 51 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle diameter of the second metal-containing material was adjusted to the size shown in Table 4. The results are shown in Table 4.

[Examples 52-58: Preparation of compositions 52-58]
Compositions 52 to 58 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle size of the second metal-containing material was adjusted to the size shown in Table 4. The results are shown in Table 4.

[Examples 59-65: Preparation of compositions 59-65]
Compositions 59 to 65 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle diameter of the second metal-containing material was adjusted to the size shown in Table 4. The results are shown in Table 4.

[Examples 66 to 72: Preparation of compositions 66 to 72]
Compositions 66 to 72 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle size of the inorganic material (1) and the second metal-containing material was adjusted to the size described in Table 4. did. The results are shown in Table 4.

[Examples 73 to 79: Preparation of compositions 73 to 79]
Compositions 73 to 79 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle diameters of the inorganic material (1) and the second metal-containing material were adjusted to the sizes shown in Table 4. did. The results are shown in Table 4.

[Examples 80-86: Preparation of compositions 80-86]
Compositions 80 to 86 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle diameters of the inorganic substance (1) and the second metal-containing material were adjusted to the sizes shown in Table 4. did. The results are shown in Table 4.

[Examples 87-93: Preparation of compositions 87-93]
Compositions 87 to 93 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle diameter of the inorganic material (1) and the second metal-containing material was adjusted to the size shown in Table 4. did. The results are shown in Table 4.

Examples 94-100: Preparation of Compositions 94-100
Compositions 94 to 100 were prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle diameters of the inorganic substance (1) and the second metal-containing material were adjusted to the sizes shown in Table 4. did. The results are shown in Table 4.

[Examples 101 to 107: Preparation of compositions 101 to 107]
Composition 101-in the same manner as in Examples 24-30 except that the type and content of the inorganic substance (1) and the average particle size of the second metal-containing material were changed to the type and content shown in Table 4. Each 107 was prepared and evaluated. The results are shown in Table 4.
In addition, the inorganic substance (1) used in Examples 101 to 107 is a silver-supported zeolite in which the average particle size is controlled to 0.3 μm (“Zeol 4A” manufactured by Nakamura Chokyu Co., Ltd., water dilution: solid content concentration 19 mass%). Is.

[Examples 108 to 114: Preparation of compositions 108 to 114]
The type and content of the inorganic substance (1) were changed to those shown in Table 4, and the content and the average particle size of the inorganic substance (2) were changed to those shown in Table 4. Compositions 108 to 114 were prepared and evaluated in the same manner as in Examples 24 to 30 except for the above. The results are shown in Table 4.
The inorganic substance (1) used in Examples 108 to 114 is a silver-supported zirconium phosphate having an average particle size controlled to 1.0 μm (“NOVALON AG300” manufactured by Toagosei Co., Ltd., solid content concentration 100% by mass). ..

[Examples 115-121: Preparation of compositions 115-121]
Compositions 115 to 121 were prepared and evaluated in the same manner as in Examples 31 to 37, except that the ethanol concentration was adjusted to the amount shown in Table 4. The results are shown in Table 4.

[Examples 122 to 128: Preparation of compositions 122 to 128]
Compositions 122 to 128 were prepared and evaluated in the same manner as in Examples 87 to 93, except that the ethanol concentration was adjusted to the amount shown in Table 4. The results are shown in Table 4.

[Examples 129 to 135: Preparation of compositions 129 to 135]
Compositions 129 to 135 were prepared and evaluated in the same manner as in Examples 101 to 107, except that the ethanol concentration was adjusted to the amount shown in Table 4. The results are shown in Table 4.

Examples 136-142: Preparation of Compositions 136-142
Compositions 136 to 142 were prepared and evaluated in the same manner as in Examples 108 to 114, except that the ethanol concentration was adjusted to the amount shown in Table 4. The results are shown in Table 4.

[Examples 143-149: Preparation of Compositions 143-149]
Examples except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4 and the type and content of the second metal inclusion was adjusted to the amount described in Table 4 Compositions 143-149 were prepared and evaluated in the same manner as 24-30. The results are shown in Table 4.
The second metal-containing material used in Examples 143-149 is copper-supporting polymer particles (corresponding to an organic material containing the second metal) having an average particle size controlled to 0.6 μm.
The copper-supported polymer particles were manufactured by the following method and used.

(Copper-supported polymer particles)
Water was removed by drying the copper oxide particles (“Copper (II) oxide copper OXIDE” manufactured by Kanto Chemical Co., Ltd.) under reduced pressure at a low temperature of 4 ° C. for 40 hours. Next, the dried copper oxide particles were dispersed by diluting with water 10 times, and then wet-milled using a bead mill. The obtained dispersion liquid was dried under reduced pressure at 50 ° C. for 5 hours to prepare CuO powder having an average particle size of 30 nm.

In a container, 150 g of polymer particles (“Eposter 100W” manufactured by Nippon Shokubai Co., Ltd., average particle size: 150 nm) aqueous dispersion (solid content concentration 0.1% by mass) were stirred, while a silicate compound (“MKC manufactured by Mitsubishi Chemical Corporation” (Registered trademark) Silicate MS51 ") (0.1 g) was added and the mixture was stirred for 20 minutes. Next, 50 g of a particle size-controlled copper oxide (“Copper (II) COPER OXIDE” manufactured by Kanto Chemical Co., Inc.) aqueous dispersion (solid content concentration 0.01% by mass: average particle size 30 nm) was added to the stirred product, The mixture was stirred for another 20 minutes to obtain a dispersion F.
Next, the obtained dispersion liquid F was centrifuged to precipitate the copper-supported polymer particles. The copper-supported polymer particles were separated by filtration and naturally dried under reduced pressure to obtain copper-supported polymer particles. As observed by an optical microscope, the copper-supported polymer particles have a structure in which copper oxide particles are supported on the surface of the polymer particles, and at least one region on the surface of the polymer particles is a silane compound condensed. It was confirmed that a film of the compound was formed. The copper-supporting polymer particles were prepared in two sizes by adjusting the dispersion time, that is, an average particle size of 0.6 μm and an average particle size of 0.3 μm.

[Examples 150 to 156: Preparation of compositions 150 to 156]
Examples except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4 and the type and content of the second metal inclusion was adjusted to the amount described in Table 4 Compositions 150-156 were prepared and evaluated in the same manner as 24-30. The results are shown in Table 4.
The second metal-containing material used in Examples 150 to 156 is copper-supporting polymer particles (corresponding to an organic material containing the second metal) whose average particle size is controlled to 0.3 μm.

Examples 157-163: Preparation of Compositions 157-163
Examples except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4 and the type and content of the second metal inclusion was adjusted to the amount described in Table 4 Compositions 157-163 were prepared and evaluated in the same manner as 24-30. The results are shown in Table 4.
The second metal-containing material used in Examples 157 to 163 is copper oxide particles (corresponding to the inorganic material (2)) having an average particle size controlled to 0.03 μm.

Examples 164-170: Preparation of Compositions 164-170
Examples except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4 and the type and content of the second metal inclusion was adjusted to the amount described in Table 4 Compositions 164-170 were prepared and evaluated in the same manner as 24-30. The results are shown in Table 4.
The second metal-containing material used in Examples 164 to 170 is copper-supporting polymer particles (corresponding to an organic material containing the second metal) having an average particle size controlled to 0.6 μm.

[Examples 171 to 177: Preparation of compositions 171 to 177]
Examples except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4 and the type and content of the second metal inclusion was adjusted to the amount described in Table 4 Compositions 171 to 177 were prepared and evaluated in the same manner as in 24 to 30, respectively. The results are shown in Table 4.
The second metal-containing material used in Examples 171 to 177 is copper-supporting polymer particles (corresponding to an organic material containing the second metal) having an average particle size controlled to 0.3 μm.

Examples 178-184: Preparation of Compositions 178-184
Compositions 178 to 184 were prepared and evaluated in the same manner as in Examples 94 to 100, except that the content of the hydrophilic component (MKC silicate) was adjusted to the amount shown in Table 4. The results are shown in Table 4.

[Examples 185-191: Preparation of compositions 185-191]
Compositions 185 to 191 were prepared and evaluated in the same manner as in Examples 178 to 184, except that the content of the hydrophilic component (MKC silicate) was adjusted to the amount shown in Table 4. The results are shown in Table 4.

[Examples 192-198: Preparation of compositions 192-198]
Compositions 192 to 198 were prepared and evaluated in the same manner as in Examples 94 to 100, except that the content of the dispersant was adjusted to the amount shown in Table 4. The results are shown in Table 4.

Examples 199-205: Preparation of Compositions 199-205
Compositions 199 to 205 were prepared and evaluated in the same manner as in Examples 94 to 100, except that the content of the dispersant was adjusted to the amount shown in Table 4. The results are shown in Table 4.

Examples 206-212: Preparation of Compositions 206-212
Zirconium phosphate (“NS-10” manufactured by Toagosei Co., Ltd.) whose average particle size was controlled to 0.8 μm was further added as the second metal-containing material in the compounding amount shown in Table 4, and the ethanol concentration was shown in Table 4. Compositions 206 to 212 were prepared and evaluated in the same manner as in Examples 31 to 37, except that the concentrations were adjusted to those described in. The results are shown in Table 4.

[Examples 213 to 219: Preparation of compositions 213 to 219]
Example 87, except that zirconium phosphate having an average particle size controlled to 0.8 μm (“NS-10” manufactured by Toagosei Co., Ltd.) was further added as the second metal-containing material in the compounding amount shown in Table 4. Compositions 213 to 219 were prepared and evaluated in the same manner as described above. The results are shown in Table 4.

[Example 220: Preparation of composition 220]
Aluminum silicate (“NS-20” manufactured by Toagosei Co., Ltd.) whose average particle diameter was controlled to 0.15 μm was used as the second metal-containing material 1, and the average particle diameter was 0.8 μm as the second metal-containing material 2. A composition 220 was prepared and evaluated in the same manner as in Example 219, except that the controlled zirconium phosphate (“NS-10” manufactured by Toagosei Co., Ltd.) was not added. The results are shown in Table 4.

[Comparative Example 8: Preparation of composition R8]
Composition R8 was prepared and evaluated in the same manner as in Example 30 except that the second metal-containing material was not added. The results are shown in Table 4.

[Comparative Example 9: Preparation of composition R9]
Composition R9 was prepared and evaluated in the same manner as in Example 26 except that the second metal-containing material was not added. The results are shown in Table 4.

[Comparative Example 10: Preparation of composition R10]
Composition R10 was prepared and evaluated in the same manner as in Example 44 except that the second metal-containing material was not added. The results are shown in Table 4.

[Comparative Example 11: Preparation of composition R11]
Composition R11 was prepared and evaluated in the same manner as in Example 40 except that the second metal-containing material was not added. The results are shown in Table 4.

[Comparative Example 12: Preparation of composition R12]
Composition R12 was prepared and evaluated in the same manner as in Example 103, except that the second metal-containing material was not added. The results are shown in Table 4.

[Comparative Example 13: Preparation of composition R13]
Composition R13 was prepared and evaluated in the same manner as in Example 110, except that the second metal-containing material was not added. The results are shown in Table 4.

[Comparative Examples 14 and 15: Preparation of Compositions R14 and R15]
Composition R14 and composition R19 were prepared and evaluated in the same manner as in Example 24 and Example 26, respectively, except that silver-supported glass (“Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd.) was not added. .. The results are shown in Table 4.

[Comparative Examples 16 and 17: Preparation of Compositions R16 and R17]
Composition R16 and composition R17 were prepared and evaluated in the same manner as in Example 52 and Example 54, respectively, except that silver-supported glass (“Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd.) was not added. .. The results are shown in Table 4.

[Comparative Examples 18 and 19: Preparation of Compositions R18 and R19]
Composition R18 and composition R19 were prepared and evaluated in the same manner as in Example 88 and Example 89, respectively, except that silver-supported glass ("Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd.) was not added. .. The results are shown in Table 4.

[Comparative Examples 20 and 21: Preparation of compositions R20 and R21]
Composition R20 and composition R21 were prepared and evaluated in the same manner as in Example 143 and Example 145, respectively, except that silver-supported glass ("Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd.) was not compounded. .. The results are shown in Table 4.

[Comparative Examples 22 and 23: Preparation of Compositions R22 and R23]
Composition R22 and composition R23 were prepared and evaluated in the same manner as in Example 150 and Example 152, except that silver-supported glass (“Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd.) was not added. .. The results are shown in Table 4.

[Comparative Examples 24 and 25: Preparation of Compositions R24 and R25]
Composition R24 and composition R25 were respectively prepared and evaluated in the same manner as in Example 157 and Example 159, except that silver-supported glass (“Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd.) was not added. .. The results are shown in Table 4.

[Comparative Example 26: Preparation of composition R26]
Composition R26 was prepared in the same manner as in Example 206, except that silver-supported glass (“Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd.) and copper-supported glass (“NS-20C” manufactured by Toagosei) were not mixed. Prepared and evaluated. The results are shown in Table 4.

[Comparative Example 27: Preparation of composition R27]
Composition R27 was prepared in the same manner as in Comparative Example 26 except that aluminum silicate was used instead of zirconium phosphate (“NS-20” manufactured by Toagosei Co., Ltd. in which the average particle size was controlled to the size shown in the table). It was prepared and evaluated, and the results are shown in Table 4.

Table 4 is shown below.
In the table, "silver-supporting glass" is "Bacterite MP-103DV (solid content 25.3% by mass)" manufactured by Fuji Chemical Co., Ltd., whose average particle size is controlled to the size described in the table. The inorganic carrier of "Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd. corresponds to phosphate glass.
In the table, "copper-supported glass" is "NS-20C" (solid content 100% by mass) manufactured by Toagosei Co., Ltd. whose average particle size is controlled to the size described in the table. The inorganic carrier of "NS-20C" manufactured by Toagosei corresponds to aluminum silicate glass.
The "silver-supporting zeolite" in the table is "Zeol 4A" (solid content 19%) manufactured by Nakamura Cemented Carbide Co., Ltd. whose average particle size is controlled to the size described in the table.
In the table, "silver-supported zirconium phosphate" is "NOVALON AG300" (solid content 100% by mass) manufactured by Toagosei Co., Ltd. whose average particle size is controlled to the size described in the table.
In the table, "copper oxide" is copper oxide (solid content 100% by mass) in which the average particle size is controlled to the size described in the table.
"Zirconium phosphate" in the table is "NS-10" (solid content 100% by mass) manufactured by Toagosei Co., Ltd. in which the average particle size is controlled to the size described in the table.
"Aluminum silicate" in the table is "NS-20" (solid content 100% by mass) manufactured by Toagosei Co., Ltd. whose average particle size is controlled to the size described in the table.

From the results of Examples 24 to 100, it was confirmed that the deodorant properties of the formed films were more excellent when the average particle size was 1.2 μm or less for both the silver-supported glass and the copper-supported glass.
Among them, from the results of Examples 52 to 72, when one of the silver-supported glass and the copper-supported glass has an average particle size of 1.2 μm or less, and the other has an average particle size of 0.9 μm or less, It was confirmed that the formed film had more excellent deodorant properties. In particular, either the silver-supported glass or the copper-supported glass has an average particle size of 1.2 μm or less, and the other has an average particle size of 0.6 μm or less, or the silver-supported glass and It was confirmed that when the average particle size of each of the copper-supported glasses was 0.9 μm or less, the deodorant property of the formed film was more excellent.
In addition, among them, from the results of Examples 73 to 93, when the average particle diameter of both silver-supported glass and copper-supported glass is 0.5 μm or less (preferably either one of silver-supported glass and copper-supported glass). It was confirmed that the formed film has a better deodorizing property when the average particle size of is less than 0.5 μm and the other average particle size is less than 0.3 μm).
From the results of Examples 94 to 100, among others, when the average particle diameter of both silver-supported glass and copper-supported glass is 0.3 μm or less, the deodorant property of the formed film tends to be more excellent. Was confirmed.

  Further, from the comparison between Examples 94 to 100 and Examples 101 to 107, it was confirmed that when the inorganic carrier of the inorganic substance (1) was glass, the deodorant property of the formed film was more excellent.

  From the comparison of Examples 24 to 100 and Examples 143-177, when the inorganic substance (1) is silver-supporting glass and the second metal-containing material is copper-supporting glass, the deodorant property of the formed film is It was confirmed that there was a tendency to be superior.

Further, from the comparison between Examples 31 to 37 and Examples 115 to 121, and the comparison between Examples 87 to 93 and Examples 122 to 128, when the ethanol concentration in the composition is 45% by mass or less, it is formed. It was confirmed that the deodorizing property of the film tends to be more excellent.
On the other hand, from the comparison between Examples 101 to 107 and Examples 129 to 135, and the comparison between Examples 116 to 114 and Examples 136 to 142, when the ethanol concentration in the composition is 5% by mass or more, it is formed. It was confirmed that the deodorizing property of the film tends to be more excellent.

  Further, from the comparison between Examples 94 to 100 and Examples 192 to 205, when the content of the dispersant in the composition is 15% by mass or more based on the total solid content of the composition (Examples 192 to 192). It was confirmed that the formed film tends to have a better deodorizing property.

  In addition, from the comparison between Examples 178 to 191 and Examples 94 to 100, it was confirmed that when the composition contained a hydrophilic component, the deodorant property and antibacterial property of the formed film were more excellent.

[Reference Example 1: Preparation of Reference Composition 1]
Water was removed by drying the copper oxide particles (“Copper (II) oxide copper OXIDE” manufactured by Kanto Chemical Co., Ltd.) under reduced pressure at a low temperature of 4 ° C. for 40 hours. Next, the dried copper oxide particles were dispersed by diluting with water 10 times, and then wet-milled using a bead mill. The obtained dispersion liquid was dried under reduced pressure at 50 ° C. for 5 hours to prepare CuO powder having an average particle size of 30 nm.

  In a container, 150 g of polymer particles (“Eposter 100W” manufactured by Nippon Shokubai Co., Ltd., average particle size: 150 nm) aqueous dispersion (solid content concentration 0.1% by mass) were stirred, while a silicate compound (“MKC manufactured by Mitsubishi Chemical Corporation” (Registered trademark) Silicate MS51 ") (0.1 g) was added and the mixture was stirred for 20 minutes. Next, 50 g of a particle size-controlled copper oxide (“Copper (II) COPER OXIDE” manufactured by Kanto Chemical Co., Inc.) aqueous dispersion (solid content concentration 0.01% by mass: average particle size 30 nm) was added to the stirred product, The mixture was stirred for another 20 minutes to obtain Dispersion G.

Next, the obtained dispersion liquid G was centrifuged to precipitate the copper-supported polymer particles. The copper-supported polymer particles were separated by filtration and naturally dried under reduced pressure to obtain copper-supported polymer particles. As observed by an optical microscope, the copper-supported polymer particles have a structure in which copper oxide particles are supported on the surface of the polymer particles, and at least one region on the surface of the polymer particles is a silane compound condensed. It was confirmed that a film of the compound was formed.
The copper-supported polymer particles had an average particle size of 0.6 μm.

In the obtained dispersion liquid G, copper-supported glass (“NS-20C” manufactured by Toagosei: As a first metal inorganic carrier: the inorganic carrier of “NS-20C” manufactured by Toagosei corresponds to aluminum silicate glass. ) 0.1 g was added and stirred to obtain Reference Composition 1.
The obtained reference composition 1 of Reference Example 1 contains a first metal organic carrier, a second metal inorganic carrier, a silicate compound as a hydrophilic component, and a solvent.

(Average particle size of the first metal inorganic carrier and the first metal organic carrier)
The average particle size of the first metal inorganic carrier and the first metal organic carrier was measured by observation using an electron microscope. The specific measurement method is as described above.

  By the same method as in Example 1, the obtained reference composition 1 of reference example 1 was evaluated. The results are shown in Table 5.

[Reference Example 2]
Reference composition 2 of reference example 2 was prepared in the same manner as reference composition 1 of reference example 1 except that MKC silicate MS51 was not used.
By the same method as in Example 1, the obtained reference composition 1 of reference example 1 was evaluated. The results are shown in Table 5.

  The "copper-supported glass" in Table 5 is "NS-20C" manufactured by Toagosei Co., Ltd., whose average particle size was controlled to the size described in the table. In addition, the inorganic carrier of "NS-20C" manufactured by Toagosei corresponds to aluminum silicate.

Claims (41)

An inorganic material containing a first metal;
A component containing at least one second metal 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;
And a solvent.   An inorganic substance containing the first metal, a metal-carrying inorganic substance comprising a simple substance of the first metal, an oxide of the first metal, and an inorganic carrier and the first metal supported on the inorganic carrier. The composition according to claim 1, which is at least one selected from the group consisting of carriers.   The inorganic substance containing the second metal is a metal-supporting inorganic substance including a simple substance of the second metal, an oxide of the second metal, and an inorganic carrier and the second metal supported on the inorganic carrier. The composition according to claim 1, which is at least one selected from the group consisting of carriers.   The composition according to any one of claims 1 to 3, wherein the component containing the second metal is an inorganic substance containing the second metal.   The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and an average particle of either one of the inorganic substance containing the first metal and the inorganic substance containing the second metal. The diameter is 1.2 μm or less, and the other average particle diameter is 0.6 μm or less, or the average of both the inorganic substance containing the first metal and the inorganic substance containing the second metal. The composition according to claim 4, which has a particle size of 0.9 μm or less.   The composition of any one of claims 1-5, wherein the first metal is silver and the second metal is copper.   7. The inorganic substance containing the first metal is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier, according to claim 1. The composition as described.   The inorganic substance containing the second metal is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, according to any one of claims 1 to 7. The composition as described.   The composition according to claim 7, wherein the first inorganic carrier is glass.   The composition according to claim 8, wherein the second inorganic carrier is glass.   The inorganic material containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic material containing the second metal is supported on the glass and the glass. The composition according to any one of claims 4 to 6, which is a copper-supporting glass containing copper.   The composition according to any one of claims 1 to 11, which further comprises a hydrophilic component selected from the group consisting of a hydrophilic binder precursor and a hydrophilic binder.   The composition according to claim 12, 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. An inorganic material containing a first metal;
A component containing at least one second metal 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. Yes, the membrane.   An inorganic substance containing the first metal, a metal-carrying inorganic substance comprising a simple substance of the first metal, an oxide of the first metal, and an inorganic carrier and the first metal supported on the inorganic carrier. The membrane according to claim 14, which is at least one selected from the group consisting of carriers.   The inorganic substance containing the second metal is a metal-supporting inorganic substance including a simple substance of the second metal, an oxide of the second metal, and an inorganic carrier and the second metal supported on the inorganic carrier. The membrane according to claim 14, which is at least one selected from the group consisting of carriers.   The film according to any one of claims 14 to 16, wherein the component containing the second metal is an inorganic substance containing the second metal.   The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and an average particle of either one of the inorganic substance containing the first metal and the inorganic substance containing the second metal. The diameter is 1.2 μm or less, and the other average particle diameter is 0.6 μm or less, or the average of both the inorganic substance containing the first metal and the inorganic substance containing the second metal. The film according to claim 17, wherein the particle size is 0.9 μm or less.   The film according to any one of claims 14 to 18, wherein the first metal is silver and the second metal is copper.   The inorganic substance containing the first metal is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier, according to any one of claims 14 to 19. The described membrane.   The inorganic material containing the second metal is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, according to any one of claims 14 to 20. The described membrane.   The membrane according to claim 20, wherein the first inorganic carrier is glass.   The membrane according to claim 21, wherein the second inorganic carrier is glass.   The inorganic material containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic material containing the second metal is supported on the glass and the glass. The film according to any one of claims 17 to 19, which is a copper-supporting glass containing copper.   The film according to any one of claims 14 to 24, which further contains a hydrophilic binder.   26. The hydrophilic binder is at least one selected from the group consisting of a hydrolyzate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a hydrolytic condensate thereof, or a hydrophilic polymer. The described membrane.   A substrate with a film, comprising the substrate and the film according to any one of claims 14 to 26. Applying a composition according to any one of claims 1 to 13 containing a hydrophilic binder precursor to the surface of a substrate to form a composition layer;
And a step of curing the composition layer to obtain a film.   A method for producing a substrate with a film, comprising the step of applying the composition according to any one of claims 1 to 13 containing a hydrophilic binder to the surface of the substrate to form a film.   A base material, an inorganic material containing a first metal, disposed on or within the base material, and an inorganic material containing a second metal different from the first metal, and the second material. A component containing at least one second metal selected from the group consisting of metal-containing organic substances, and a modified base material.   A base material, an inorganic material containing a first metal, disposed on or within the base material, and an inorganic material containing a second metal different from the first metal, and the second material. A modified substrate having a hydrophilic binder and a component containing at least one second metal selected from the group consisting of organic substances containing metal.   An inorganic substance containing the first metal, a metal-carrying inorganic substance comprising a simple substance of the first metal, an oxide of the first metal, and an inorganic carrier and the first metal supported on the inorganic carrier. The modified substrate according to claim 30 or 31, which is at least one selected from the group consisting of carriers.   The inorganic substance containing the second metal is a metal-supporting inorganic substance including a simple substance of the second metal, an oxide of the second metal, and an inorganic carrier and the second metal supported on the inorganic carrier. The modified substrate according to claim 30 or 31, which is at least one selected from the group consisting of carriers.   The modified substrate according to any one of claims 30 to 33, wherein the component containing the second metal is an inorganic substance containing the second metal.   The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and an average particle of either one of the inorganic substance containing the first metal and the inorganic substance containing the second metal. The diameter is 1.2 μm or less, and the other average particle diameter is 0.6 μm or less, or the average of both the inorganic substance containing the first metal and the inorganic substance containing the second metal. The modified base material according to claim 34, having a particle size of 0.9 µm or less.   The modified substrate according to any one of claims 30 to 35, wherein the first metal is silver and the second metal is copper.   The inorganic material containing the first metal is a silver-supporting inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier, according to any one of claims 30 to 36. The modified base material described.   The inorganic substance containing the second metal is a copper-supporting inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier, according to any one of claims 30 to 37. The modified base material described.   38. The modified substrate of claim 37, wherein the first inorganic carrier is glass.   39. The modified substrate of claim 38, wherein the second inorganic carrier is glass.   The inorganic material containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic material containing the second metal is supported on the glass and the glass. The modified base material according to any one of claims 34 to 36, which is a copper-supported glass having copper supported on.