WO2019013227A1

WO2019013227A1 - Composition, film, film-attached base material, method for producing film-attached base material, and modified base material

Info

Publication number: WO2019013227A1
Application number: PCT/JP2018/026100
Authority: WO
Inventors: 三ツ井　哲朗
Original assignee: 富士フイルム株式会社
Priority date: 2017-07-10
Filing date: 2018-07-10
Publication date: 2019-01-17
Also published as: CN110809405A; JPWO2019013227A1

Abstract

A problem to be solved by the present invention is to provide a composition which makes it possible to form a film having excellent antibacterial properties and excellent deodorant properties and a modified base material. Another problem to be solved by the present invention is to provide a film, a film-attached base material, a method for producing a film-attached base material, and a modified base material. The composition according to the present invention contains: an inorganic material containing a first metal; at least one component containing a second metal that is different from the first metal, wherein the component is selected from the group consisting of an inorganic material containing the second metal and an organic material containing the second metal; and a solvent.

Description

Composition, film, film-coated substrate, method of producing film-coated substrate, and modified substrate

The present invention relates to a composition, a film, a film-coated substrate, a method of producing a film-coated substrate, and a modified substrate.

Antimicrobial films comprising antimicrobial particles and a binder are known. The antibacterial film has a function of suppressing bacterial growth on its surface.
For example, in Patent Document 1, “1) glass particles, ceramic particles, or porous silica gel particles having metal ions having antibacterial activity, and 2) organosilane capable of hydrolysis and polycondensation or partial hydrolysis thereof A composition for antibacterial coating based on a substance.

JP-A-8-27404

The inventor of the present invention made and examined an antibacterial film formed using the composition for antibacterial coating described in Patent Document 1, and revealed that the deodorizing performance did not meet the recent requirement level. .

Then, this invention makes it a subject to provide the composition which can form the film | membrane or modified base material which has the outstanding antimicrobial property and the outstanding deodorizing property.
Another object of the present invention is to provide a film, a film-coated substrate, a method of producing a film-coated substrate, and a modified substrate.

As a result of intensive studies to achieve the above problems, the present inventor has found that the problems can be achieved by the following configuration.

[1] An inorganic substance containing a first metal
An inorganic substance containing a second metal different from the first metal, and a component containing at least one second metal selected from the group consisting of an organic substance containing the second metal;
A composition containing a solvent.
[2] The inorganic substance containing the first metal includes the simple substance of the first metal, the oxide of the first metal, and the inorganic support and the first metal supported on the inorganic support The composition according to [1], which is at least one selected from the group consisting of metal-supported inorganic carriers.
[3] The inorganic substance containing the second metal comprises the single substance of the second metal, the oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support The composition according to [1], which is at least one selected from the group consisting of metal-supported inorganic carriers.
[4] The composition according to any one of [1] to [3], wherein the component containing the second metal is an inorganic material containing the second metal.
[5] The inorganic substance containing the first metal and the inorganic substance containing the second metal are particles, and either the inorganic substance containing the first metal or the inorganic substance containing the second metal Any of the inorganic substance containing an average particle size of 1.2 μm or less and the other average particle size of 0.6 μm or less, or the inorganic substance containing the first metal and the inorganic substance containing the second metal The composition according to [4], wherein the average particle size is also 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 silver-supported inorganic support according to [1], wherein the inorganic substance containing the first metal is a silver-supported inorganic support having a first inorganic support and silver supported on the first inorganic support. The composition as described in any one.
[8] The copper-supported inorganic support according to [1], wherein the inorganic substance containing the second metal is a copper-supported inorganic support having a second inorganic support and copper supported on the second inorganic support. The composition as described in any one.
[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 silver-supporting glass having glass and silver supported on the glass, and the inorganic material containing the second metal is glass and the glass The composition according to any one of [4] to [6], which is a copper-supported glass having carried copper.
[12] The composition according to any one of [1] to [11], further comprising 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 substance containing a first metal
An inorganic substance containing a second metal different from the first metal, and a component containing at least one second metal selected from the group consisting of an organic substance containing the second metal Do the membrane.
[15] The inorganic substance containing the first metal includes the simple substance of the first metal, the oxide of the first metal, and the inorganic support and the first metal supported by the inorganic support. The membrane according to [14], which is at least one selected from the group consisting of metal-supported inorganic carriers.
[16] The inorganic substance containing the second metal comprises the single substance of the second metal, the oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support The membrane according to [14], which is at least one selected from the group consisting of metal-supported 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 either the inorganic substance containing the first metal or the inorganic substance containing the second metal Any of the inorganic substance containing an average particle size of 1.2 μm or less and the other average particle size of 0.6 μm or less, or the inorganic substance containing the first metal and the inorganic substance containing the second metal The film according to [17], which also has an average 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] The silver-supported inorganic support according to [14], wherein the inorganic substance containing the first metal is a silver-supported inorganic support having a first inorganic support and silver supported on the first inorganic support. The membrane according to any one.
[21] The copper-supported inorganic support according to [14], wherein the inorganic substance containing the second metal is a copper-supported inorganic support having a second inorganic support and copper supported on the second inorganic support. 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 material containing the first metal is silver-supporting glass having glass and silver supported on the glass, and the inorganic material containing the second metal is glass and the glass The film according to any one of [17] to [19], which is a copper-supported glass having carried copper.
[25] The film according to any one of [14] to [24], further comprising a hydrophilic binder.
[26] The hydrophilic binder is at least one member 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] membrane.
[27] A membrane-coated substrate comprising a substrate and the membrane according to any one of [14] to [26].
[28] A composition layer is formed by applying the composition according to any one of [1] to [13] containing a hydrophilic binder precursor on the surface of a substrate,
Curing the composition layer to obtain a film.
[29] A method for producing a film-coated substrate, comprising the step of applying the composition according to any one of [1] to [13] containing a hydrophilic binder on the surface of the substrate to form a film. .
[30] A base material, an inorganic substance containing a first metal disposed on or in the base material, and an inorganic substance containing a second metal different from the first metal, and the above A modified substrate comprising: 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 substance containing a first metal disposed on or in the base material, and an inorganic substance containing a second metal different from the first metal, and the above A modified substrate comprising: a component containing at least one second metal selected from the group consisting of an organic material containing a second metal, and a hydrophilic binder.
[32] The inorganic substance containing the first metal includes the simple substance of the first metal, the oxide of the first metal, and the inorganic support and the first metal supported by the inorganic support. The modified substrate according to [30] or [31], which is at least one selected from the group consisting of metal-supported inorganic carriers.
[33] The inorganic substance containing the second metal comprises the simple substance of the second metal, the oxide of the second metal, and an inorganic support and the second metal supported by the inorganic support The modified substrate according to [30] or [31], which is at least one selected from the group consisting of metal-supported inorganic carriers.
[34] The modified substrate according to any one of [30] to [33], wherein the component containing the second metal is an inorganic material containing the second metal.
[35] One of the inorganic substance containing the first metal and the inorganic substance containing the second metal is a particle, and the inorganic substance containing the first metal and the inorganic substance containing the second metal Any of the inorganic substance containing an average particle size of 1.2 μm or less and the other average particle size of 0.6 μm or less, or the inorganic substance containing the first metal and the inorganic substance containing the second metal The modified substrate according to [34], which also has 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] The silver-supported inorganic carrier according to any one of [30] to [36], wherein the inorganic substance containing the first metal is a silver-supported inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier. The modified base material as described in any one.
[38] The copper-supported inorganic support according to [30], wherein the inorganic substance containing the second metal is a copper-supported inorganic support having a second inorganic support and copper supported on the second inorganic support. The modified base material as described in any one.
[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 substance containing the first metal is silver-supporting glass having glass and silver supported on the glass, and the inorganic substance containing the second metal is glass and the glass The modified substrate according to any one of [34] to [36], which is a copper-supported glass having supported and supported copper.

ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the film | membrane or modified base material which has the outstanding antimicrobial property and the outstanding deodorizing property can be provided. Further, according to the present invention, it is possible to provide a film, a film-coated substrate, a method of producing a film-coated substrate, and a modified substrate.

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

〔Composition〕
The above composition (hereinafter also referred to as “composition according to the embodiment”) is a first metal-containing inorganic substance (hereinafter also referred to as “inorganic substance (1)” or “first metal-containing substance”), and the above At least one first 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 metal-containing component (hereinafter also referred to as "second metal-containing material") and a solvent.
In addition, in this specification, when only calling it a "metal", a metal simple substance (metal simple particle), a metal ion, and the metal atom contained in a compound shall be included.

The film or modified substrate formed by the above composition is excellent in antibacterial property and deodorizing property by the presence of the above-mentioned inorganic substance (1) and the above-mentioned second metal-containing substance.

Also, as described later, the second metal-containing substance is an inorganic substance (2), and at least one selected from the group consisting of the inorganic substance (1) and the inorganic substance (2) is in the form of particles, and the average When the particle size is 1.2 μm or less, a film or modified substrate having better antibacterial properties and better deodorizing properties can be obtained.
Among others, as described later, the inorganic substance (1) is a silver-supporting inorganic support having a first inorganic support and silver supported on the first inorganic support, and an inorganic (2) And a film or a modifying group having more excellent antibacterial properties and more excellent deodorizing properties, in the case where the carrier is a copper-supported inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier. The material is obtained. For example, with regard to urinary odor, an enzyme generated from bacteria decomposes urea and becomes an ammonia source during the mechanism of urinary odor generation, and copper is presumed to exhibit excellent enzyme degradability and exhibits high deodorizing ability. On the other hand, silver is known to exhibit high antibacterial properties. For this reason, it is presumed that when the membrane or modified substrate contains a silver-supporting inorganic carrier and a copper-supporting inorganic carrier, it exhibits better antibacterial properties and better deodorizing. Furthermore, although copper is known not only to exhibit high deodorizing ability as described above but also to exhibit high antibacterial properties, the inventor of the present invention has made various investigations that silver and copper have different mechanisms. It is speculated that it exhibits antibacterial activity. As a result, when the membrane or the modified substrate contains a silver-supporting inorganic carrier and a copper-supporting inorganic carrier, each of the two antibacterial mechanisms of copper and silver simultaneously acts on the bacteria, and each is used alone and In comparison, it is considered that remarkably superior antibacterial properties can be obtained.
Furthermore, the inorganic support in at least one of the silver-supporting inorganic support and the copper-supporting inorganic support (preferably a copper-supporting inorganic support, more preferably a silver-supporting inorganic support and a copper-supporting inorganic support) is amorphous (amorphous) In this case, the metal ions are more easily released from the first metal and the second metal, and thus the above-mentioned effect is further enhanced.

Although the use in particular of the said composition is not restrict | limited, For example, it can apply to the diaper used at a care setting site, and the antimicrobial effect and the deodorizing effect which were excellent with respect to urine odor are exhibited.
Urine odor is caused by substances contained in urine, such as ammonia and trimethylamine. When the urine absorbed in the diaper is left for a long time, the odor of the diaper becomes stronger because the above-mentioned substances responsible for the urine odor are further increased by the action of bacteria.
On the other hand, when the membrane formed by the above composition is formed at the site touched by the urine in the diaper, bacterial growth and enzymatic degradation of the urine material by the bacteria are suppressed, so the ammonia and trimethylamine described above The increase of substances such as That is, the increase in odor is suppressed. Furthermore, the deodorizing effect is stably sustained over a long period of time from when urine is absorbed in the diaper.
In addition, the said effect is similarly acquired by the modification | requirement base material mentioned later formed using the said 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, but is not limited to, Escherichia (eg, E. coli etc.), Staphylococcus (eg, S. aureus etc.), Klebsiella (eg, K. oxytoca, K. pneumoniae etc.), Serratia (eg, S. marcescens), Citrobacter (eg, C. freundii, C. diversus etc.), Enterobacter (eg, E. aerogenes, E. cloacae), Proteus (eg, P. mirabilis, Those having a bactericidal (including bactericidal) and / or bacteriostatic effect against bacteria of P. vulgaris etc.), Pseudomonas sp. (Eg P. aeruginosa etc.), and Morganella sp. (Eg M. morganii etc.) preferable.

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

The inorganic substance (1) contains a first metal. The form of the inorganic substance (1) is not particularly limited, and a first metal simple substance (metal simple particle), an ion of the first metal, and an inorganic compound containing the first metal (definition of the compound: by chemical change The pure substance which can be divided into two or more elements alone may be used, or a mixture thereof. In addition, the inorganic substance (1) may be a complex of an inorganic compound and a first metal. As the complex, for example, an inorganic carrier, and a first metal (for example, a first metal single particle (metal single particle), a first metal ion, and a first metal) supported on the inorganic carrier are mentioned. (A compound containing the first metal may specifically include an inorganic compound containing the first metal) (a compound containing the first metal may be any one of the compounds containing the first metal). Hereinafter, it may be referred to as "first metal-supported inorganic carrier".
Among them, the inorganic substance (1) is a simple substance (particle) of a first metal, an ion of a first metal, an oxide of a first metal, and an inorganic substance supporting a first metal, from the viewpoint that the effect of the present invention is more excellent. At least one member selected from the group consisting of carriers is preferable, and at least one member selected from the group consisting of a single metal particle (particles) of a first metal, an oxide of a first metal, and a first metal-supported inorganic carrier is More preferably, the first metal-supported inorganic support is more preferred.

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

The type of inorganic support of the first metal-supported inorganic support 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, hydrated bismuth oxide, hydrated zirconium oxide, and hydrotalcite; activated carbon; metal; etc. Be
In the present specification, the inorganic support of the first metal-supported inorganic support may be referred to as the "first inorganic support".

The inorganic carrier may be crystalline or non-crystalline (amorphous), but is preferably non-crystalline, more preferably glass. As a material which can comprise glass, a silicate, borosilicate, and phosphate etc. are mentioned, for example, Especially, a silicate is preferable and aluminum silicate is more preferable.

The aluminum silicate may be natural or synthetic. As aluminum silicate, the compound represented by 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. Among them, n is preferably 8 to 15 and m is preferably 3 to 15.

Among the above-mentioned inorganic carriers, inorganic substances (1) include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel and the like (for example, zirconium phosphate and the like) Aluminum silicate etc. can also be used.

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

When the inorganic substance (1) is a particle, the average particle diameter of the particles of the inorganic substance (1) is not particularly limited, but in general, it is 0.01 μm or more, preferably 0.2 μm or more. Further, the upper limit thereof is not particularly limited, and for example, 10 μm or less is mentioned, and 5.0 μm or less is preferable. Among them, 3.0 μm or less is preferable, 1.5 μm or less is more preferable, 1.2 μm or less is more preferable, 0.9 μm or less is further more preferable, 0.6 μm or less is particularly preferable, 0.5 μm or less is most preferable And 0.3 μm or less is more preferable.
When the sedimentation and the transparency of the composition are taken into consideration, the smaller the average particle diameter of the inorganic substance (1), the better the dispersibility, and as a result, the transparency of the composition tends to be higher. In the point which the transparency of a composition is more excellent, 0.5 micrometer or less is preferable and, as for the average particle diameter of inorganic substance (1), 0.4 micrometer or less is more preferable.

The average particle size of the particles of the inorganic substance (1) can be measured by observation using an electron microscope. Specifically, for the particles of the inorganic substance (1), the above-mentioned average particle diameter is a primary particle and a secondary particle (Note that “secondary particle” is an aggregate formed by fusion or contact of primary particles with each other) 90% of the total number of particles excluding the 5% of the number of particles on the small diameter side and the 5% of the particles on the large diameter side of the total particle number. The average particle diameter in the range of That is, the average particle size is a value determined from primary particles and secondary particles. Moreover, a diameter means the circumscribed circle equivalent diameter of particle | grains.
In addition, when there is no big difference in the particle shape of the particles of the inorganic substance (1), 50% volume cumulative diameter (D50) is measured three times using a laser diffraction / scattering type particle size distribution analyzer manufactured by Horiba, Ltd. The average value of the values measured three times may be substituted as the average particle diameter.

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

As a formation method of an inorganic substance (1), any of a breakdown method (for example, a grinding method) and a buildup method may be used.
Examples of the method of grinding the inorganic substance (1) include dry grinding and wet grinding. In dry grinding, for example, a mortar, a jet mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, and a bead mill are suitably used. In wet grinding, various ball mills, high-speed rotary grinders, jet mills, bead mills, ultrasonic homogenizers, high-pressure homogenizers, and the like are suitably used. For example, in a bead mill, the average particle size can be controlled by adjusting the diameter, type, and mixing amount of beads serving as media.

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

The inorganic substance (1) may be used alone or in combination of two or more.
The content of the inorganic substance (1) in the composition (the total content of the inorganic substance (1) in the case where a plurality of the inorganic substances (1) is contained) is not particularly limited, but 0.001 to 55 mass with respect to the total solid content of the composition % Is preferable, 0.001 to 50% by mass is more preferable, and 0.01 to 40% by mass is more preferable.

Further, the content of the metal in the inorganic substance (1) is not particularly limited, but, for example, when the inorganic substance (1) is a metal-supported carrier, the content of the metal is 0.001 to 30% by mass is preferable, and 0.01 to 10% by mass is more preferable. In addition, when multiple inorganic substances (1) are contained in a composition, it is preferable that total content of a metal is the said numerical range.

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

The content of the second metal-containing material in the composition is not particularly limited, but is preferably 0.01 to 50% by mass, preferably 0.01 to 40% by mass, and more preferably 0.1 to 35% by mass. 0.1 to 30% by mass is more preferable, and 0.1 to 10% by mass is particularly preferable.
The second metal-containing material may be used alone or in combination of two or more. When using 2 or more types of 2nd metal containing things together, it is preferable that total content is in the said range.

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

The second metal is not particularly limited, and silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel and the like can be mentioned, and silver, copper, 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 single metal (particle) of a second metal, an ion of a second metal, or an inorganic compound containing a second metal, and a mixture thereof It may be The inorganic substance (2) may be a complex of an inorganic compound and a second metal. The complex includes, for example, an inorganic carrier, and a second metal (second metal single particle (metal single particle) supported on the inorganic carrier, ions of the second metal, and a second metal. A metal supported carrier (hereinafter referred to as “any of the compounds (the compound containing the second metal may specifically include an inorganic compound containing the second metal)) Also referred to as "second metal-supported inorganic carrier".
The inorganic substance (2) is at least one selected from the group consisting of a single metal (particle) of a second metal, an oxide of a second metal, and a second metal-supported inorganic carrier in the viewpoint of being superior by the effect of the present invention Is more preferable, and the second metal-supported inorganic carrier is more preferable.

As the inorganic carrier of the second metal-supporting inorganic carrier, the same one as the inorganic carrier of the first metal-supporting inorganic carrier can be used. In the present specification, the inorganic support of the second metal-supported inorganic support may be referred to as "second inorganic support".

Specific examples of the second metal-supporting inorganic support are preferably metal-supporting zeolite, metal-supporting apatite, metal-supporting glass, metal-supporting zirconium phosphate, or metal-supporting calcium silicate supporting a second metal, metal-supporting glass Is more preferred.

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

Examples of the second metal-containing organic substance include salts of the second metal. As a second metal salt, acetate, acetylacetonate, metal acetylide, (cis, cis-1,5-cyclooctadiene) -1,1,1,5,5,5-hexafluoroacetylacetonate Diethyldithiocarbamate, 7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedionate, lactate, oxalate, perfluorobutyrate, perfluoro Propionate, picrate, propionate, sulfadiazine salt, p-toluenesulfonate, trifluoromethanesulfonate, trifluoroacetate and the like can be mentioned.

The organic substance containing the second metal may be a complex of an organic compound and the second metal. The complex contains, for example, an organic carrier, and a second metal (second metal single particle (metal single particle) supported on the organic carrier, ions of the second metal, and a second metal. A metal-supported carrier comprising any of the compounds (specifically, the second metal-containing compound includes an inorganic compound containing the second metal), or An organic-inorganic composite comprising an inorganic compound containing a metal of 2 and an organic compound arranged so as to cover the above-mentioned inorganic compound is preferable, and in particular, a metal having 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-supported organic carrier include polymer particles.

As a specific example of the second metal-supporting organic support, for example, a polymer particle supporting a second metal selected from the group consisting of copper particles and copper oxide particles (hereinafter, also referred to as “copper-supporting polymer”) is It can be mentioned.
The average particle diameter of the copper particles and the copper oxide particles is preferably 90 nm or less, more preferably 70 nm or less, and still more preferably 50 nm or less, in that the effect of the present invention is more excellent. The lower limit is not particularly limited, and is, for example, 1 nm or more.
The average particle diameter of the said copper particle and said copper oxide particle can use the measuring method of the average particle diameter of the particle | grains of the inorganic substance (1) demonstrated already.
From the image of the electron microscope, when there is no significant change in the particle shape in the state in which the copper particles or copper oxide particles in the copper-supporting polymer particles and the copper particles or copper oxide particles alone are dispersed, The average particle size may be substituted by a measurement value by dynamic light scattering using a dispersion of particles only. In this case, the average particle size can be measured by dynamic light scattering using a particle size distribution measuring device by laser diffraction or the like.

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, and is, for example, 1 nm or more. The average primary particle diameter of the copper particles and the copper oxide particles is more preferably 5 to 90 nm, and still more preferably 5 to 50 nm, in that the effects of the present invention are more excellent.
The “average primary particle size” means that the diameter of each primary particle is measured from the image of the electron microscope, and the number of primary particles on the smallest diameter side among the total number of primary particles is 5% and the diameter is the largest. It is a value obtained by averaging the diameters of primary particles in the range of 90% excluding the primary particle number 5%. Here, the diameter means the circumscribed circle equivalent diameter of primary particles.

In the copper-supporting polymer particles, the average particle diameter of the polymer particles is preferably 100 to 1000 nm, and more preferably 100 to 800 nm.
The average particle diameter of the polymer particles can be measured using the method of measuring the average particle diameter of the particles of the inorganic substance (1) described above.
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, EPOPER 050W and 100W manufactured by Nippon Shokubai can be used.

In the copper-supported polymer particles, the ratio of polymer particles to copper particles and copper oxide particles (mass of polymer particles / total mass of copper particles and copper oxide particles) is not particularly limited, but it is more excellent in antibacterial properties. In terms of mass ratio, for example, the range of 1 / 0.00001 to 1 / 10,000 is preferable, and the range of 1 / 0.0001 to 1 / 10,000 is more preferable.

In addition, the copper-supporting polymer particles may have a coating formed of a silane compound formed on at least a part of the surface of the polymer particles as a carrier. As a silane compound, it is obtained by condensing the silicate type compound mentioned later, for example.

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

Among them, as the second metal-containing material, the inorganic material (2) and the second metal-supporting organic carrier are preferable. The second metal-supported inorganic support or the second metal-supported organic support is more preferable, and the second metal-supported inorganic support is more preferable.

When the second metal-containing material is a particle, the average particle diameter of the second metal-containing material is not particularly limited, but is, for example, 4.0 μm or less, preferably 2.0 μm or less, and more preferably 1.5 μm or less preferable. Above all, 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, 0.6 μm or less Is particularly preferably 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less, and most preferably 0.15 μm or less. The lower limit is preferably 0.01 μm or more, more preferably 0.10 μm or more.
In addition, the measurement and adjustment method of the average particle diameter of the particle | grains of the inorganic substance (1) already demonstrated can be used for measurement and adjustment of the average particle diameter of the particle | grains of a 2nd metal inclusion.

When the second metal-containing material is a particle, the aspect ratio is not particularly limited, but is preferably 1 to 40, and more preferably 2 to 20.
The aspect ratio is calculated by the following method. First, using an electron microscope, of two parallel straight lines circumscribing the second metal inclusion, select two parallel straight lines with the largest distance between straight lines, and then select the distance between the two parallel straight lines. The major axis of the second metal inclusions. Next, among two parallel straight lines that are orthogonal to the major axis and circumscribed to the second metal inclusion, two parallel straight lines with the smallest distance between straight lines are selected, and between the two parallel straight lines Of the second metal inclusion as the minor axis of the second metal inclusion. The ratio of the major axis to the obtained minor axis (major axis / minor axis) is taken as the specific aspect ratio. The above aspect ratio can be obtained by performing this operation on arbitrary 100 or more second metal-containing substances and arithmetically averaging the obtained specific aspect ratios.

As an example of the suitable form of the above-mentioned composition, an inorganic substance (2) is included as the 2nd metal content thing of the above-mentioned, and the above-mentioned inorganic substance (1) and the above-mentioned inorganic substance (2) are particles. The average particle size is preferably 1.5 μm or less for any of the above 2), and it is more preferable that the average particle size is 1.2 μm or less for both the inorganic substance (1) and the inorganic substance (2). More preferably the average particle diameter of either one of the inorganic substance (2) or less is 1.2 μm or less and the average particle diameter of the other is 0.9 μm or less, and the inorganic substance (1) and the inorganic substance (2) Either one of the average particle sizes is 1.2 μm or less, and the other is 0.6 μm or less, or the average particle size of either the inorganic substance (1) or the inorganic substance (2) is 0 .9 μm or less is particularly preferable More preferably, the average particle size of either the inorganic substance (1) or the inorganic substance (2) is 0.5 μm or less, and the average particle size of either the inorganic substance (1) or the inorganic substance (2) is 0. It is most preferable that the average particle diameter is 5 μm or less, and the other is 0.3 μm or less, and it is more preferable that the average particle diameter of both the inorganic substance (1) and the inorganic substance (2) is 0.3 μm or less .

As another example of a suitable form of the above-mentioned composition, a form containing a silver content thing as the above-mentioned inorganic substance (1), and a copper content thing as the above-mentioned 2nd metal content thing is 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 at the point where the deodorizing property and the antibacterial property are more excellent (content of copper in copper-containing material 800 or less is preferable, 350 or less is more preferable, 300 or less is still more preferable, 0.1 or more is preferable, and 5.0 or more is more preferable, for example.

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 in the form of particles from the viewpoint of deodorant and antibacterial properties. The average particle diameter is preferably 1.5 μm or less for both the silver-containing material and the copper-containing material, and it is more preferable that the average particle diameter is 1.2 μm or less for both the silver-containing material and the copper-containing material. More preferably, the average particle diameter of either the silver-containing material or the copper-containing material is 1.2 μm or less, and the other average particle diameter is 0.9 μm or less, and the silver-containing material and the copper-containing material The average particle diameter of either one is 1.2 μm or less, and the other average particle diameter is 0.6 μm or less, or the average particle diameter of either of the silver-containing material and the copper-containing material is 0. It is particularly preferable that the thickness is 9 μm or less, and it is preferable to contain silver and copper. It is more preferable that the average particle size of any of the objects is particularly 0.5 .mu.m or less, and the average particle size of any one of the silver-containing material and the copper-containing material is 0.5 .mu.m or less and the other It is most preferable that the average particle diameter is 0.3 μm or less, and most preferable that the average particle diameter of any of the silver-containing material and the copper-containing material is 0.3 μm or less.
In the above embodiment, the silver-containing inorganic carrier having the first inorganic carrier and the silver supported on the first inorganic carrier is preferable, and the silver-containing glass as the inorganic material (1) is more preferable. In addition, a copper-containing material as the second metal-containing material is supported by a copper-supporting inorganic carrier having a second inorganic carrier and copper supported by the second inorganic carrier, and an organic carrier and the organic carrier. One or more selected from the group consisting of copper-supporting organic supports having copper and copper are preferred, and copper-supporting inorganic supports having a second inorganic support and copper supported on the second inorganic support are more preferred.

Moreover, as another example of the preferred embodiment of the above composition, a silver-supporting inorganic carrier is contained as the inorganic substance (1), and a copper-containing substance (preferably, the second inorganic carrier and the above-mentioned second metal-containing substance). And at least one selected from the group consisting of a copper-supported inorganic carrier having copper supported on the inorganic carrier of 2 and a copper-supported organic carrier having an organic carrier and copper supported on the organic carrier, More preferably, a form containing a copper-supported 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 the suitable form of the said composition, the said inorganic substance (1) is a silver carrying | support inorganic support | carrier, and the form whose 2nd metal content thing is a zirconium phosphate or phosphate glass is mentioned.
In the case of the above embodiment, the average particle diameter of the inorganic substance (1) is preferably 0.01 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, particularly preferably 0.5 μm or more, and 10 μm or less Preferably, 5.0 μm or less is more preferable. The average particle diameter of the second metal-containing material is preferably 4.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.5 μm or less, particularly preferably 1.0 μm or less, and 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 diameter of 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 the suitable form of the said composition, the said inorganic substance (1) is a zirconium phosphate or phosphate glass, a 2nd metal containing material is a copper containing material (preferably, 2nd inorganic support | carrier, And at least one selected from the group consisting of a copper-supporting inorganic support having copper supported on the second inorganic support, and a copper-supporting organic support having an organic support and copper supported on the organic support. More preferably, the form which is a copper carrying | support inorganic support | carrier which has the 2nd inorganic support | carrier and the copper carry | supported by the said 2nd inorganic support | carrier is mentioned.
In the case of the above embodiment, the average particle diameter of the inorganic substance (1) is preferably 4.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.5 μm or less, particularly preferably 1.0 μm or less The following is most preferable, 0.01 μm or more is preferable, and 0.1 μm or more is more preferable. In addition, the average particle diameter of the second metal-containing material is preferably 0.01 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, particularly preferably 0.5 μm or more, and preferably 10 μm or less. 0 μm or less is more preferable. Among them, the average particle diameter of 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, based on the total solid content of the composition. % By mass is more preferred.
The hydrophilic component may be used alone or in combination of two or more. When two or more hydrophilic components are used in combination, the total content is preferably within the above range.

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

Furthermore, since the hydrophilic binder has hydrophilicity, it has high affinity with odorants such as ammonia and trimethylamine. Therefore, the hydrophilic binder also has the function of retaining and diffusing the odorous substance on the surface of the membrane to increase the chance of contact between the odorous substance and the inorganic substance (1) and the second metal-containing substance. Moreover, according to the composition containing a hydrophilic component, excellent deodorizing property is likely to be maintained for a long time.
In addition, a hydrophilic binder precursor means the material which can form a hydrophilic binder by hardening reactions, such as a condensation and superposition | polymerization.
Moreover, a hydrophilic binder means the material which can form a hydrophilic film | membrane which can support an inorganic substance (1) and a 2nd metal content thing. When a film made of the above hydrophilic binder is formed on a glass substrate as the hydrophilic binder, for example, one having a water contact angle of 60 ° or less is preferable, and one having a water contact angle of 50 ° or less is preferable. The lower limit of the water contact angle is not particularly limited, but generally 5 ° or more is preferable.
The water contact angle is measured based on the static droplet method of JIS R 3257: 1999. For measurement, FAMMS DM-701 manufactured by Kyowa Interface Science Co., Ltd. is used.

The hydrophilic component is not particularly limited, but a silicate compound, a monomer having a hydrophilic group (hereinafter, also referred to as a "hydrophilic monomer"), and a polymer having a hydrophilic group (hereinafter referred to as "hydrophilic group") And at least one selected from the group consisting of "hydrophilic polymers".
In addition, the monomer which has a hydrophilic group means the compound which has a hydrophilic group and a polymeric group. The hydrophilic monomer is polymerized to form a hydrophilic polymer when the composition contains a polymerization initiator described later.
Below, a silicate type compound, a hydrophilic monomer, and a hydrophilic polymer are each demonstrated.

(Silicate compounds)
In the present specification, a 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 hydrolytic condensate thereof, and, for example, At least 1 sort (s) selected from the group which consists of a compound represented by 1), its hydrolyzate, and its hydrolysis-condensation product is 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, tetra-t And butyl silicate, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, and propyl butyl silicate.

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

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

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

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

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

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

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

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

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

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

<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% by mass in that the composition has more excellent coatability. And more preferably adjusted to 0.01 to 10% by mass, and further preferably adjusted to 0.1 to 5.0% by mass.
The solvents may be used alone or in combination of two or more. When two or more solvents are used in combination, the total content is preferably within the above range.

The solvent is not particularly limited and includes water and / or an organic solvent. As the organic solvent, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenylethyl alcohol, capryl alcohol, lauryl alcohol, and Alcohol solvents such as myristyl alcohol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene Glycol monobutyl ether, diethylene glycol Glycol ether solvents such as butyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; cyclopentane, cyclohexane, methyl Alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether and di-n-butyl ether; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate , Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hex acetate Ester solvents such as ethyl propionate and butyl propionate; hydrophilic solvents such as 10% denatonium alcohol solution, geraniol, octaacetylated sucrose, brucine, linalool, linalyl acetate, and acetic acid; Be As a solvent, alcohol is preferable, and ethanol or isopropyl alcohol is more preferable, since it is easy to suppress elution of the metal contained in the inorganic substance (1) and the second metal-containing substance into the solvent.

In the above composition, the content of the alcohol is preferably 5% by mass or more based on the total mass of the composition, from the viewpoint of suppressing the sedimentation of the particulate matter and the point that the deodorizing property of the formed film is more excellent. 10 mass% or more is preferable. Although the upper limit value is not particularly limited, for example, 99% by mass or less is preferable, 70% by mass or less is more preferable, 60% by mass or less is more preferable, and 45% by mass or less is particularly preferable.

When the solvent contains an 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, based on the total mass of the solvent. Preferably, 5 to 90% by mass is more preferable, and 5 to 80% by mass is particularly preferable.

<Other ingredients>
The above composition may contain other components within the scope of the effects of the present invention. As other components, for example, deodorant, antibacterial agent, ultraviolet light absorber, preservative, pH adjuster, antifoamer, polymerization initiator, catalyst, photocatalytic material, surfactant, filler, antiaging agent And well-known additives such as antistatic agent, flame retardant, adhesion imparting agent, leveling agent, matting agent, light stabilizer, dye, pigment, dispersing agent, fragrance, film forming agent, and dispersion stabilizer. .
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.
As a polymerization initiator, a thermal polymerization initiator, a photoinitiator, etc. are mentioned, for example.
Examples of the polymerization initiator include aromatic ketones such as benzophenone and phenylphosphine oxide; α-hydroxyalkylphenone compounds (manufactured by BASF, IRGACURE 184, 127, 2959, and DAROCUR 1173); phenylphosphine oxide Compounds (monoacyl phosphine oxide: IRGACURE TPO manufactured by BASF, bisacyl phosphine oxide: IRGACURE 819 manufactured by BASF);
Among them, a photopolymerization initiator is preferable from the viewpoint of reaction efficiency.

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

(Dispersant)
When at least one of the inorganic substance (1) and the second metal-containing substance is in the form of particles, the composition preferably contains a dispersant.
The dispersant is not particularly limited, and known dispersants can be used.
The dispersant is preferably a nonionic or anionic dispersant. From the viewpoint of the affinity to the inorganic substance (1) and the second metal-containing substance, a dispersant (anionic dispersant) having an anionic polar group such as a carboxy group, a phosphate group, and a hydroxyl group is more preferable.
A commercial item can be used as an anionic dispersing agent. As a specific example, the trade names DISPERBYK (registered trademark) -110, -111, -116, -140, -161, -162, -163, -164, -170, -170, -171, -174,- Preferred 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 with respect to the total solid content of the composition. The lower limit value is not particularly limited, but is, for example, 0.01% by mass or more, and preferably 1.0% by mass or more, and more preferably 15% by mass or more, in that the deodorizing property of the formed film is more excellent.
The dispersant may be used alone or in combination of two or more. When two or more dispersants are used in combination, the total content is preferably within the above range.

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

The catalyst is not particularly limited, and examples thereof include alkali catalysts and organic metal catalysts.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide and tetramethyl ammonium hydroxide.
As the organic metal catalyst, aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), and aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate), And zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate); titanium chelate compounds such as titanium tetrakis (acetylacetonate); and titanium bis (butoxy) bis (acetylacetonate); and dibutyltin diacetate And dibutyltin dilaurate, and organic tin compounds such as dibutyltin diacrylate and the like.
Among them, an organometallic catalyst is preferable as a catalyst in that a composition having more excellent effects of the present invention can be obtained, 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 catalyst may be used alone or in combination of two or more. When two or more types of catalysts are used in combination, the total content is preferably within the above range.

(Surfactant)
The composition may contain a surfactant. The surfactant has the effect of improving the coatability of the composition.
The surfactant is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
The content of the surfactant is not particularly limited, but is preferably 0.01 parts 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 10 parts by mass or less is preferable, 5 parts by mass or less is more preferable, and 4 parts by mass or less with respect to 100 parts by mass of the total solid content of the composition. More preferable.
The surfactant may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that those total content is in the said range.

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

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

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

(Film-forming agent)
The composition may contain a film-forming agent. In the present specification, the film-forming agent does not include the above-described silicate-based compound, hydrophilic monomer, and hydrophilic polymer.
As a film-forming agent, a thermoplastic resin is mentioned. The film-forming agent functions as a binder, for example, when a film described later is formed.
The thermoplastic resin is 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, fluorine resin, 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, resin composed of cycloolefin copolymer, 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.
In addition, a thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.
The content of the thermoplastic resin may be appropriately adjusted according to the type of the thermoplastic resin etc., but for example, it is preferably 30% by mass or less and more preferably 20% by mass or less based on the total solid content of the composition. .

(Antimicrobial agent and deodorant)
The composition includes, for example, quaternary ammonium salts, phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, pyridine compounds, triazine compounds, benzoisothiazoline compounds as antibacterial agents And an organic antibacterial agent such as isothiazoline compound may be contained.

In addition, the composition contains, as a deodorant, inorganic acids such as phosphoric acid and nitric acid or salts thereof; organic acids such as malic acid, citric acid and ascorbic acid or salts thereof; dibutylhydroxytoluene; butylhydroxyanisole; hinokitiol Phenol; and compounds containing a phenolic hydroxyl group such as tannic acid, kakitannin and tea tannin may be included.

Examples of the inorganic acid include phosphoric acid, sulfurous acid, sulfuric acid, and alkali metal salts thereof.
Examples of the organic acids 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, meldrum's acid, glutamic acid, ferula Examples thereof include acids, picric acid, and aspartic acid, and alkali metal salts thereof and the like. Among organic acids, the larger the molecular weight, the less likely it is to volatilize, so the pH of the film surface formed using the composition is easily maintained at 6.5 or less.

As a deodorizer, malic acid or citric acid is preferable, and malic acid is more preferable, from the viewpoint of being less volatile and being more deodorizing.
In addition, when a compound having an antioxidant function (for example, sulfite, ferulic acid, dibutylhydroxytoluene, butylhydroxyanisole, and ascorbic acid, etc.) is used as a deodorant, the inorganic substances (1) and the second substances described above are used. Deterioration of the metal-containing component is more easily suppressed, and the antibacterial and deodorizing properties of the film are more excellent.
Moreover, it is also preferable to use together the deodorant which has an antioxidant function, and deodorizers other than the deodorant which has an antioxidant function as a deodorant. When the deodorant having the antioxidant function and the deodorant other than the antioxidant having the antioxidant function are used in combination, the antibacterial property and the deodorizing property of the film are maintained for a longer period of time.

<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 and the like in the 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 still more preferably 6.0 to 8.0.
When the composition contains, for example, a component that dissolves in acid or alkali as the inorganic substance (1) and the second metal-containing component, or a component that easily deteriorates, the composition has a pH within the above range Has a better effect of the present invention.
In addition, the method of mix | blending an acid or an alkali with the said composition as a method of adjusting the pH of a composition is mentioned.
The pH can be measured under a 25 ° C. environment using a commercially available pH measurement meter (eg, pH meter HM-30R manufactured by Toa DK Co., Ltd.).

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

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

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

<Method of producing composition>
In addition, the said composition can contain other additives as needed in the range with the effect of this invention.
The composition can be prepared by appropriately mixing the above-described essential components and optional components. In addition, the order in particular of mixing of the said component is not restrict | limited.

<Application of Composition>
The composition can be used to form a film.
The method for forming the film is not particularly limited, but a method (coating method) in which the composition is applied to a desired substrate or article to form a coating, and then dried or cured to form a film is preferable.
The method for applying the composition to the desired substrate or article is not particularly limited. For example, spray, roll coater, gravure coater, screen, spin coater, flow coater, inkjet, electrostatic coating, and wipe can be mentioned. Among them, a spray or a wipe is preferable, and a wipe is more preferable, in that a film can be formed on the surface of an existing article to perform processing (on-demand processing) according to demand.
There is no particular limitation on the method of forming a film by wiping, and known methods can be used. For example, the following method may be mentioned. First, the composition is impregnated into a base fabric such as a non-woven fabric, and then the surface of the substrate or article is wiped with the base fabric. Thereby, the coating film by the said composition is formed in a base material or the article surface. Thereafter, the formed coating is dried or cured to obtain a film.

Moreover, according to the said composition, as mentioned later, the modified base material excellent in deodorizing property and antibacterial property can be formed. When the above-mentioned composition is used to obtain a modified substrate, the composition may further contain 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.

〔film〕
The film of the present invention contains the inorganic substance (1) and the second metal inclusion.

<Inorganic substance (1)>
As an inorganic substance (1), it is the same as that of the inorganic substance (1) contained in the said composition, and its preferable form is also the same.

<Second metal inclusions>
As a 2nd metal content, it is the same as that of the 2nd metal content contained in the said composition, and its preferable 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 in which a hydrolyzable group is bonded to a silicon atom, and a hydrolytic condensate thereof; At least one selected from the group consisting of a hydrolyzate of a compound having a degradable group bonded thereto, and a hydrolytic condensate thereof is preferred.
In addition, the preferable form of the compound which the hydrolysable group couple | bonded with the silicon atom, and the preferable form of the polymer which has a hydrophilic group are as having mentioned above.

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

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

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

<PH of membrane>
The membrane surface pH of the membrane is typically preferably 7.0 or less, and particularly preferably 6.5 or less, because it is more excellent in the deodorizing property against malodorous substances derived from urine and feces such as ammonia and trimethylamine. .0 or less is more preferable, and 4.5 or less is still more preferable. The lower limit of the membrane surface pH of the membrane is not particularly limited, but is preferably 1.0 or more.
In the present specification, for the film surface pH of the film, 0.02 mL of droplets (pure water) are dropped on the film surface, and after 1 minute, the pH of the droplets is adjusted to the pH of Horiba, Ltd. It is a value determined by measuring using a meter LAQUA F-72.

As described later, the membrane can be applied to applications such as diapers. At this time, when an odor substance-containing liquid such as urine adheres to the film surface, when the film surface pH falls within the above numerical range (preferably, the film surface pH is 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 the deodorizing property are more excellent.

As an example of a film | membrane whose film surface pH is the said numerical range, the film | membrane which contains an inorganic substance (1), a 2nd metal containing material, and an organic acid is mentioned, for example. Since the organic acid has low volatility, it adheres to the hydrophilic binder in the dry state. When an odor substance-containing liquid such as urine adheres to this film surface, the organic acid on the film surface is dissolved by the odor substance-containing liquid, and the film surface pH of the film tends to be in the above range. In this way, in the state before the odorant-containing liquid is attached, the film surface pH does not become too low, and the metal in the inorganic substance (1) and the second metal-containing substance contained in the film is less likely to deteriorate.
Further, as another example of the film having a film surface pH in the above-mentioned numerical range, a film which is dissolved in the odorant-containing liquid, a compound having a pH adjusting function included in the film, etc. (may be the above-mentioned organic acid) And a method in which the microcapsules are contained in the membrane. When the odorant-containing liquid adheres to the film surface of the film containing the above-mentioned microcapsule, the film of the microcapsule 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 be in the above range. . Also, in this case, the film surface pH 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 is less likely to deteriorate .

[Substrate with membrane]
The film-coated substrate according to the embodiment of the present invention has a substrate and the above-mentioned film. The film-coated substrate may be a laminate having a substrate and a film, and may have a film on the surface on one side of the substrate, or have a film on the surface on both sides of the substrate You may

<Base material>
The substrate plays a role of supporting the membrane, and the type is not particularly limited.
The shape of the substrate is not particularly limited, and examples thereof include plate, film, sheet, tube, fiber, and particles.
It does not restrict | limit especially as a material which comprises a base material, For example, a metal, glass, ceramics, and plastics (resin) etc. are mentioned. Among them, plastic is preferable in terms of handleability. In other words, as the substrate, a resin substrate is preferable.

[Method of producing a film-coated substrate]
The method for producing a film of the present invention corresponds to a method for producing a film using the composition described above, and has the following steps.
(1) When a composition contains a hydrophilic binder precursor as a hydrophilic component, it has following process A and the following process B.
(2) When a composition contains a hydrophilic binder as a hydrophilic component, it has the following process 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 Hereinafter, about Step A and Step B explain.

(Step A)
Step A is a step of applying the composition to the surface of the substrate to form a composition layer. It does not restrict | limit especially as a method to apply | coat a composition on the surface of a base material, A well-known application method can be used.
As a method of applying a composition to the surface of a substrate, the method mentioned above is mentioned.

The thickness of the composition layer is not particularly limited, but a dry thickness of 0.001 to 10 μm is preferable.
In addition, after the composition is applied, heat treatment may be performed to remove the solvent. The conditions for the heat treatment in that case are not particularly limited. For example, the heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 15 to 600 seconds.
In addition, as a base material which can be used in the process A, it is the same as that of the form of the base material already demonstrated.

(Step B)
Step B is a step of curing the composition layer to obtain a film. That is, in this step, the hydrophilic binder precursor contained in the composition layer is converted to 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, but includes, for example, a form in which the composition layer is cured by irradiation with ultraviolet rays of 100 to 600 mJ / cm ² with an ultraviolet lamp.
In the case of ultraviolet irradiation, ultraviolet light and the like emitted from light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc and a metal halide lamp can be used.
The temperature of the heat treatment is not particularly limited, but for example, 50 to 150 ° C. is preferable, and 80 to 120 ° C. is more preferable.

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

Although the shape in particular of the said base material is not restrict | limited, Plate shape, a film shape, sheet shape, tube shape, fiber shape etc. are mentioned. The term "fiber-like" as used herein refers to fibers and structures such as a two-dimensional structure and a three-dimensional structure formed by fibers (for example, a cloth-like body such as a woven or knitted fabric and a non-woven fabric).
It does not restrict | limit especially as a material which comprises the said base material, For example, natural resin, a synthetic resin, etc. are mentioned.

Hereinafter, an embodiment of a modification substrate is 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 a base material is a fiber structure, the form which has a fiber structure, the inorganic substance (1) adhering to the surface of the said fiber structure, and a 2nd metal containing component as said modification base material, and a fiber structure The form which has an inorganic substance (1) and a 2nd metal containing component in the inside of the body and the said fiber structure is mentioned. 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 based on the mass of the fiber or fiber structure % Is preferred.
There is no particular limitation on the method of forming the modified substrate in which the substrate is a fiber or a fiber structure, and for example, after applying the above-described composition to a fiber or a fiber structure by a method such as impregnation and spraying, Methods of drying to form a modified substrate are included. When the above composition contains a hydrophilic binder precursor, heat treatment and / or exposure treatment may be performed.
Moreover, as another example of the method for forming a modified base material that is a fiber structure, for example, a slurry is prepared by mixing a fiber material such as pulp and the above-described composition, and wet sheet making using this slurry as a raw material According to the method, there is a method of forming a modified substrate having a fibrous structure, an inorganic substance (1) disposed in the fibrous structure, and a component containing a second metal.

The modified substrate is, for example, a form having a molded body (for example, a sheet-like molded body) formed of a resin, an inorganic substance (1) disposed inside the molded body, and a second metal-containing component. It is also good. The resin is not particularly limited, and examples thereof include synthetic resins (water-absorbent polymers such as sodium polyacrylate). As a modification base material concerning the above-mentioned embodiment, it can form using the composition mentioned above. As a specific manufacturing method, after casting the composition described above to form a cast film, drying, heating and / or curing may be carried out. In addition, when forming the modification base material which concerns on the said embodiment using the composition mentioned above, it is preferable that a composition contains a polymer, a curable compound, etc. further. The polymer and the curable compound are not particularly limited, and examples thereof include sodium polyacrylate and the like.

<Inorganic substance (1)>
As an inorganic substance (1), it is the same as that of the inorganic substance (1) contained in the said composition, and its preferable form is also the same.
<Second metal inclusions>
As a 2nd metal content, it is the same as that of the 2nd metal content contained in the said composition, and its preferable 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 substance is the same as the preferred embodiment of the combination of the inorganic substance (1) and the second metal-containing substance in the composition described above.

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

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

[Wet wiper]
A wet wiper according to an embodiment of the present invention has a base fabric and a composition impregnated in the base fabric. The above composition is as described above.

The base fabric is not particularly limited, and may be formed of natural fibers or chemical fibers.
Natural fibers include, for example, pulp, cotton, hemp, flax, wool, camel, cashmere, mohya, silk and the like.
Materials for chemical fibers include rayon, polynozic, acetate, triacetate, nylon, polyester, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, polyalkylene para oxybenzoate, and polychlore, etc. .
Among these base fabrics, hydrophilic base fabrics are preferable in that the composition is easily impregnated. The hydrophilic base is, for example, a base containing a fiber having a hydrophilic group such as a hydroxyl group, an amino group, a carboxy group, an amido group, and a sulfonyl group. Specific examples of the hydrophilic base cloth include vegetable fibers, cotton, pulp, animal fibers, rayon, nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.
As a base fabric of the said wet wiper, a nonwoven fabric, cloth, a towel, gauze, absorbent cotton etc. may be used, and a nonwoven fabric is preferable.
The basis weight (mass per unit area) of the base fabric is preferably 100 g / m ² or less. The amount of impregnation at the time of impregnating the composition with the base fabric is preferably an amount of one or more times the mass of the base fabric.

〔spray〕
The spray which concerns on embodiment of this invention has a spray container and the composition accommodated in the said spray container. The above composition is as described above.
As a spray of this invention, the form which filled the said composition and the propellant in the predetermined | prescribed container is mentioned as an example. The propellant to be used is not particularly limited, and examples thereof include liquefied petroleum gas and the like.

[Composition (Reference Example)]
In addition, the present inventor also has excellent antibacterial properties by a composition containing a first metal-supporting inorganic carrier, a first metal-supporting organic carrier, and a solvent (hereinafter also referred to as a “composition (reference example)”). It has been found that it is possible to form a film having good properties and excellent deodorizing properties.
Here, the first metal is not particularly limited, but silver or copper is more preferable, and copper is particularly preferable.

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

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

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

The content of the first metal-supported inorganic carrier in the composition (Reference Example) is not particularly limited, but is preferably 0.01 to 40% by mass with respect to the total solid content of the composition. % By mass is more preferable, and 0.1 to 10% by mass is even more preferable.

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

The average particle size of the first metal-supporting organic carrier is not particularly limited, but generally 0.01 μm or more is preferable, 0.2 μm or more is more preferable, and 0.5 μm or more is more preferable. The upper limit thereof is preferably 3.0 μm or less, and more preferably 1.0 μm or less. When the sedimentation of the first metal-supporting organic carrier and the transparency of the composition are taken into consideration, the smaller the average particle diameter of the first metal-supporting organic carrier, the better the dispersibility, and as a result, the transparency of the composition Higher and preferred. In this case, the average particle diameter of the first metal-supported organic carrier is preferably 1.0 μm or less, more preferably 0.5 μm or less, and still more preferably 0.4 μm or less.
When the composition (Reference Example) contains a hydrophilic binder described later by setting the average particle diameter of the first metal-supporting organic carrier to the above numerical range, in a film formed using the composition (Reference Example) The first metal-supporting organic carrier can be easily fixed in the state of being exposed from the hydrophilic binder. Therefore, the metal is more easily released from the carrier, and the antibacterial property and the deodorizing property of the film are further excellent.
In addition, the measuring method of the average particle diameter of a 1st metal support organic carrier is the same as the measuring method of the average particle diameter of the inorganic substance (1) which may be contained in the composition of embodiment already demonstrated.

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% by mass, based on the total solid content of the composition, 0.01 to 40 % By mass is more preferred.

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

<Hydrophilic binder>
The composition (Reference Example) may contain a hydrophilic component.
As a hydrophilic component, it is the same as that of what was demonstrated as a hydrophilic component which may be contained in the composition of embodiment already demonstrated, and the suitable 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 may be included in the composition of the embodiment described above, and the preferred form is also the same.

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

<Method of Producing Composition (Reference Example) and Use>
The production method and use of the composition (Reference Example) are the same as those described for the production method and use of the composition of the embodiment described above, and the preferred embodiments are also the same.

[Membrane (reference example)]
In addition, the inventor of the present invention 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 deodorizing properties. We have found that it has sex.
Here, the first metal is not particularly limited, but silver or copper is more preferable, and copper is particularly preferable.

<First metal-supported inorganic carrier>
The first metal-supported inorganic carrier is the same as the first metal-supported inorganic carrier contained in the composition (the reference example) described above, and the preferred embodiment 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 (the reference example) described above, and the preferred embodiment 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 in which a hydrolyzable group is bonded to a silicon atom, and a hydrolytic condensate thereof; At least one selected from the group consisting of a hydrolyzate of a compound having a degradable group bonded thereto, and a hydrolytic condensate thereof is preferred.
In addition, the preferable form of the compound which the hydrolysable group couple | bonded with the silicon atom, and the preferable form of the polymer which has a hydrophilic group are the same as that of the composition of embodiment already demonstrated.

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

<Method of manufacturing membrane (reference example)>
The film of the present invention can be obtained, for example, by drying or curing the above composition (Reference Example). As said composition (reference example), it is as having already demonstrated.
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 film (the reference example) is obtained by setting the hydrophilic binder precursor in the composition layer to a hydrophilic binder by curing treatment of the composition layer.
On the other hand, when the hydrophilic component in the composition (Reference Example) is a hydrophilic binder, it is not necessary to carry out the curing treatment on the composition (Reference Example).

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

<PH of membrane (reference example)>
The pH on the surface of the membrane (Reference Example) is typically preferably 7.0 or less, and in particular 6.5 or less because it is more excellent in the deodorizing property against malodorous 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 membrane surface pH of the membrane (Reference Example) is not particularly limited, but is preferably 1.0 or more.
In the present specification, for the film surface pH of the film (Reference Example), 0.02 mL of droplets (pure water) were dropped on the film surface, and after 1 minute, the pH of the droplets was It is a value obtained by measurement using a pH meter LAQUA F-72 manufactured by corporation.

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

As an example of the film | membrane whose film surface pH is the said numerical range, the film | membrane containing a 1st metal support inorganic carrier, a 1st metal support organic carrier, and an organic acid is mentioned, for example. Since the organic acid has low volatility, it adheres to the hydrophilic binder in the dry state. When an odor substance-containing liquid such as urine adheres to this film surface, the organic acid on the film surface is dissolved by the odor substance-containing liquid, and the film surface pH of the film tends to be in the above range. In this way, the film surface pH does not become too low in the state before the odorant-containing liquid adheres, and the metal in the first metal-supported inorganic carrier and the first metal-supported organic carrier contained in the film is denatured. Hateful.
Further, as another example of the film having a film surface pH in the above-mentioned numerical range, a film which is dissolved in the odorant-containing liquid, a compound having a pH adjusting function included in the film, etc. (may be the above-mentioned organic acid) And a method in which the microcapsules are contained in the membrane. When the odorant-containing liquid adheres to the film surface of the film containing the above-mentioned microcapsule, the film of the microcapsule 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 be in the above range. . Also, in this case, the film surface pH does not become too low in the state before the odorant-containing liquid is attached, and the metal in the first metal-supported inorganic carrier and the first metal-supported organic carrier contained in the film is It is hard to deteriorate.

[Base with Membrane (Reference Example)]
The film-coated substrate (Reference Example) has a substrate 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 a film (reference example) on the surface of one side of the substrate. , And may have a film (Reference Example) on the surface on both sides of the substrate.

<Base material>
The substrate plays a role of supporting the membrane (reference example), and the type is not particularly limited.
As a base material, it is the same as that of the base material used with the film-coated base material of embodiment already demonstrated.

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

[Wet wiper (reference example)]
The wet wiper (Reference Example) has a base cloth and a composition (Reference Example) impregnated in the base cloth. As said composition (reference example), it is as having already demonstrated.
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 to be used is different.

[Spray (reference example)]
The spray (reference example) has a spray container and the composition (reference example) stored in the spray container. As said composition (reference example), it is as having already demonstrated.
The specific configuration of the spray (the reference example) is the same as the specific configuration of the spray according to the embodiment described above, except that the composition to be used is different.

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

Example 1 Preparation of Composition 1
60 g of pure water, 14 g of a silicate compound ("MKC (registered trademark) Silicate" MS 51 "manufactured by Mitsubishi Chemical Co., Ltd.) and aluminum chelate D (aluminium bis (ethyl acetoacetate) mono (acetyl aceto) while stirring 367 g of ethanol in a container ), Ethanol dilution: 15 g solid content concentration, 15 g nonionic surfactant ("Emarex 715" manufactured by Nippon Emulsion Co., pure water dilution: 0.5 mass% solid concentration), anionic interface After sequentially adding 10 g of an activator (sodium di (2-ethylhexyl) sulfosuccinate, pure water dilution: solid concentration 0.2% by mass), 18 g of isopropanol, a dispersant (manufactured by BYK "DISPERBYK (registered trademark)-180" Silver-supported glass particles adjusted to an average particle size of 0.3 μm (3.6 g) (Fuji Chemica Company Ltd., diluted ethanol: solids concentration 60 mass%) 2.4 g was added and stirred for 20 minutes to obtain a dispersion liquid A.
In addition, the said silver carrying | support glass particle in this dispersion liquid A corresponds to an inorganic substance (1).

In the obtained dispersion A, as a second metal-containing substance, a copper-supporting glass (corresponding to “NS-20C” manufactured by Toagosei Co., Ltd. (inorganic substance (2). Inorganic carrier of “NS-20C” manufactured by Toagosei Co., Ltd.) A composition 1 is obtained by adding and stirring 0.28 g of aluminum silicate (corresponding to aluminum silicate).
The obtained composition 1 of Example 1 contains an inorganic substance (1), a second metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.

(Average particle size of inorganic substance (1) and second metal-containing substance)
When the inorganic substance (1) and the second metal-containing substance are particles, the average particle diameter of the particles is 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 deodorizing property based on the test shown 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 per 100 cm ^{2 of} non-woven fabric. Next, the obtained non-woven fabric with composition 1 was dried at 25 ° C. for 2 days to produce a film-coated substrate 1.

(Evaluation of deodorant)
The urine having an ammonia odor was sprayed on the membrane-coated substrate 1 at 10 g and left at room temperature. The odor after 1 h and 8 h after sensory standing was evaluated sensoryily. The results are shown in Table 1.

«Evaluation criteria»
"A": Almost no odor.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": I feel an odor.
"E": strongly smells.

(Evaluation of antibacterial activity)
The antimicrobial properties of the film-coated substrate 1 were evaluated.
The evaluation of the antimicrobial property was conducted in accordance with the evaluation method described in JIS Z 2801: 2012, using E. coli and changing the contact time to the bacterial solution to 24 hours to carry out the test. The antimicrobial 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 2.5 or more "B": antibacterial activity value 1.0 or more and less than 2.5 "C": antibacterial activity value less than 1.0

(Membrane surface pH)
The antimicrobial properties of the film-coated substrate 1 were 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 Example 1, except that the second metal-containing substance was not used, and that the average particle size of the inorganic substance (1) was adjusted to the size (μm) described in Table 1. Composition R1 of 1 was prepared.
Various evaluation was implemented by the method similar to the composition 1 using obtained composition R1. 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 size of the inorganic substance (1) and the second metal-containing substance was adjusted to the size described 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 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 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
The composition R3 was prepared and evaluated in the same manner as in Example 3 except that silver supporting glass was not used. The results are shown in Table 1.

Table 1 is shown below.
The “copper-supporting glass” in Table 1 is “NS-20C” manufactured by Toagosei Co., Ltd., whose average particle diameter is controlled to the size described in the table. The inorganic carrier of "NS-20C" manufactured by Toagosei Co., Ltd. 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 have 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 substance (1) did not have the effects of the present invention.

In addition, it is found that the composition of Example 2, which contains a hydrophilic component, maintains superior deodorizing properties even after 8 hours as compared with the composition of Example 3. The

Example 4 Preparation of Composition 4
Composition 4 was prepared in the same manner as Example 1, except that the average particle size of the inorganic substance (1) and the average particle size and aspect ratio of the second metal-containing substance were adjusted to the values described in Table 2. Prepared.
The evaluation of <Evaluation B> described later was performed using the prepared composition 4 and the results are shown in Table 2. Note that <Evaluation B> described later is a more severe 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 test shown below.
First, a non-woven fabric was prepared, and the composition 4 was jetted to the non-woven fabric so that 0.1 g of the composition 4 adhered per 100 cm ^{2 of} non-woven fabric. Next, the obtained nonwoven fabric with composition 4 was dried at 25 ° C. for 2 days to produce a membrane-coated substrate 4.

(Evaluation of deodorant)
The ammonia smelling urine was sprayed on the membrane-coated substrate 4 at 10 g and left at room temperature. The odor after 1 h and 8 h after sensory standing was evaluated sensoryily. The results are shown in Table 1.

«Evaluation criteria»
"AA": A very slight odor is felt.
"A": Almost no odor.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": I feel an odor.
"E": strongly smells.

(Evaluation of antibacterial activity)
The antimicrobial properties of the film-coated substrate 4 were evaluated.
The evaluation of the antimicrobial property was conducted in accordance with the evaluation method described in JIS Z 2801: 2012, using E. coli and changing the contact time to the bacterial solution to 24 hours to carry out the test. The antimicrobial 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 2.5 or more "B": antibacterial activity value 1.0 or more and less than 2.5 "C": antibacterial activity value less than 1.0

(Membrane surface pH)
The antimicrobial properties of the film-coated substrate 4 were evaluated. The evaluation method is as described above.

Example 5 Preparation of Composition 5
The composition 5 was prepared and evaluated in the same manner as in Example 4 except that the average particle diameter and the 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
The composition 6 was prepared and evaluated in the same manner as in Example 4 except that the average particle size and the 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 7 Preparation of Composition 7
Composition 7 was prepared in the same manner as Example 4, except that the average particle size of the inorganic substance (1) and the average particle size and aspect ratio of the second metal-containing substance were adjusted to the values described in Table 2. Prepared and evaluated. The results are shown in Table 2.

In addition, the result of having implemented the evaluation B mentioned above using the composition 1 and the composition 2 which were mentioned above is also shown in Table 2.

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

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

Example 8 Preparation of Composition 8
The water content was removed by drying the copper oxide particles ("Copper (II) COPPER OXIDE" manufactured by Kanto Chemical Co., Ltd.) under reduced pressure at 4 ° C. for 40 hours at a low temperature. Next, the dried copper oxide particles were dispersed by diluting with 10 times with water, and then wet-pulverized using a bead mill. The obtained dispersion was dried at 50 ° C. for 5 hours under reduced pressure to prepare a CuO powder having an average particle diameter of 30 nm.
In addition, about the copper oxide (II) particle used for the composition 16 (Example 16) mentioned later, the method similar to copper oxide (II) used by the composition 8 except having varied the milling time and the kind of filter The particle size was controlled by

In a container, 150 g of an aqueous dispersion (solid content concentration: 0.1% by mass) of polymer particles (Nippon Shokuhin “Epoler 100 W”, average particle diameter: 150 nm) is stirred while a silicate compound (MKC Corporation “MKC” 0.1 g of (registered trademark) Silicate MS 51 ") was added and stirred for 20 minutes. Subsequently, 50 g of copper oxide ("Copper oxide (II) COPPER OXIDE" manufactured by Kanto Chemical Co., Ltd.) aqueous dispersion (solid content concentration 0.01 mass%: average particle size 30 nm) whose particle size is controlled is added to this stirred product, The mixture was further stirred for 20 minutes to obtain dispersion C.
This dispersion liquid C contains copper-supporting polymer particles (corresponding to the organic substance containing the second metal) as the second metal-containing substance.

In the column of this example, regarding the average particle diameter of the copper oxide particles and the polymer particles in the copper-supporting polymer particles, using the dispersion liquid of only the copper oxide particles and the dispersion liquid of only the polymer particles, the following dynamic The average particle size obtained by measurement by light scattering was substituted.
(Measurement of average particle size of copper oxide particles and polymer particles)
The average particle sizes of the copper oxide particles and the polymer particles in the dispersion liquid were measured by dynamic light scattering using a particle size distribution analyzer by laser diffraction.
Specifically, it was measured using a dynamic light scattering measurement apparatus (Zetasizer ZS) manufactured by Marveln. The average particle size was measured three times according to the method defined in ISO 13321 as an average value (Z-Average) of particle sizes by cumulant analysis, and an average value of values measured three times was used.

Next, the obtained dispersion C was centrifuged to precipitate 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. According to observation with an optical microscope, the copper-supporting polymer particle has a structure in which copper oxide particles are supported on the surface of the polymer particle, and a silane is formed by condensation of a silicate compound in at least one region on the surface of the polymer particle. It confirmed that the film of the compound was formed.
In addition, 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 which controlled the average particle diameter to 0.3 micrometer as an inorganic substance (1) to the obtained dispersion liquid C, and stirring it.
The zirconium phosphate corresponds to one obtained by controlling “NS-10” manufactured by Toagosei Co., Ltd. to an average particle diameter of 0.3 μm.
The obtained composition 8 of Example 8 contains an inorganic substance (1), a second metal-containing substance (an organic substance 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 deodorizing property based on the test shown below.
First, a non-woven fabric was prepared, and the composition 8 was sprayed to the non-woven fabric so that 1 g of the composition 8 was adhered per 100 cm ² . Next, the obtained nonwoven fabric with composition 8 was dried at 25 ° C. for 2 days to produce a membrane-coated substrate 8.

(Evaluation of deodorant)
The urine having an ammonia smell was sprayed on the membrane-coated substrate 8 at 10 g and left at room temperature. The odor after 1 h and 8 h after sensory standing was evaluated sensoryily. The results are shown in Table 3.

«Evaluation criteria»
"AA": I feel only a faint odor.
"A": Almost no odor.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": I feel an odor.
"E": strongly smells.

(Evaluation of antibacterial activity)
The antimicrobial properties of the film-coated substrate 8 were evaluated.
The evaluation of the antimicrobial property was conducted in accordance with the evaluation method described in JIS Z 2801: 2012, using E. coli and changing the contact time to the bacterial solution to 24 hours to carry out the test. The antimicrobial 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 2.5 or more "B": antibacterial activity value 1.0 or more and less than 2.5 "C": antibacterial activity value less than 1.0

(Membrane surface pH)
The antimicrobial properties of the film-coated substrate 8 were evaluated. The evaluation method is as described above.

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

Examples 16 and 20: Preparation of Compositions 16 and 20
Further, compositions 16 and 20 of Examples 16 and 20 were respectively prepared by the same method as that of composition 8 of Example 8 except that additives were added in the compounding amounts described in Table 3.
The obtained composition 16 and composition 20 of Example 16 and Example 20 were the inorganic substance (1), the second metal-containing substance (the organic substance containing the second metal), the silicate compound as the hydrophilic component, and Contains solvent.
Various evaluations were performed by the method similar to the composition 8 using the obtained composition 16 and the composition 20. The results are shown in Table 3.

Example 11 Preparation of Composition 11
60 g of pure water, 14 g of a silicate compound ("MKC (registered trademark) Silicate" MS 51 "manufactured by Mitsubishi Chemical Co., Ltd.) and aluminum chelate D (aluminium bis (ethyl acetoacetate) mono (acetyl aceto) while stirring 367 g of ethanol in a container ), Ethanol dilution: 15 g solid content concentration, 15 g nonionic surfactant ("Emarex 715" manufactured by Nippon Emulsion Co., pure water dilution: 0.5 mass% solid concentration), anionic interface After sequentially adding 10 g of an activator (sodium di (2-ethylhexyl) sulfosuccinate, pure water dilution: solid concentration 0.2% by mass), 18 g of isopropanol, a dispersant (manufactured by BYK "DISPERBYK (registered trademark)-180" ) 3.6 g, silver-supported glass particles whose average particle size is controlled to 0.6 μm (Fuji Chemica Company Ltd., diluted ethanol: solids concentration 60 mass%) 2.4 g was added and stirred for 20 minutes to obtain a dispersion liquid D.
In addition, the said silver carrying | support glass particle in this dispersion liquid D corresponds to an inorganic substance (1).

Composition obtained by adding 0.28 g of zirconium phosphate (corresponding to the inorganic substance (2)) whose average particle diameter is controlled to 0.3 μm as a second metal-containing substance to the obtained dispersion liquid D and stirring it. I got the object 11.
The zirconium phosphate corresponds to one obtained by controlling “NS-10” manufactured by Toagosei Co., Ltd. to an average particle diameter of 0.3 μm.
The obtained composition 11 of Example 11 contains an inorganic substance (1), a second metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed by the method similar to the composition 8 using the obtained composition 11. 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 each prepared in the same manner as Composition 11 of Example 11 except that the type and average particle diameter of the second metal-containing material were changed to the compositions described in Table 3. Prepared.
The resulting compositions 12 to 13 of Examples 12 to 13 include the inorganic substance (1), the second metal-containing substance (inorganic substance (2)), the silicate compound as a hydrophilic component, and a solvent.
Using the resulting compositions 12 to 13, 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 C was replaced with 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 by the same method as that of composition 8 using composition 14 obtained. 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 diameter of the inorganic substance (1) (silver-loaded 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 obtained composition 15 of Example 15 contains an inorganic substance (1), a second metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.
Using the obtained composition 15, various evaluations were carried out by the same method as that of the composition 8. The results are shown in Table 3.

[Examples 17, 18, 21: Preparation of Compositions 17, 18, 21]
Further, in the same manner as the composition 15 of the example 15 except that the additive is added in the compounding amount described in Table 3, the composition 17, the composition 18 of the example 17, the example 18, and the example 21 And Composition 23 was prepared respectively.
The obtained compositions 17, 18, 21 of Examples 17, 18, 21 contain an inorganic substance (1), a second metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed by the method similar to the composition 8 using the obtained compositions 17, 18, and 21. The results are shown in Table 3.

Example 19 Preparation of Composition 19
Copper-supported glass whose average particle diameter is controlled to the size listed in Table 3 as a second metal-containing substance (“NS-20C” manufactured by Toagosei Co., Ltd .: inorganic support of “NS-20C” manufactured by Toagosei) Dispersion C2 was prepared in the same manner except that 0.1 g of aluminum glass was added.
The dispersion C2 contains, as a second metal-containing substance, copper-supporting glass (corresponding to the inorganic substance (2)) and copper-supporting polymer particles (corresponding to the organic substance containing the second metal). Do.
To the obtained dispersion liquid C, 0.28 g of zirconium phosphate whose average particle diameter was controlled to 0.3 μm was added as the inorganic substance (1), and the mixture was stirred to obtain a composition 21. The obtained composition 19 of Example 19 contains an inorganic substance (1), a second metal-containing substance (inorganic substance (2), an organic substance containing a second metal), a silicate compound, and a solvent.
Various evaluations were performed by the same method as that of composition 8 using composition 19 obtained. The results are shown in Table 3.

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

Example 23 Preparation of Composition 23
In the obtained dispersion D1, as a second metal-containing substance, 0.28 g of zirconium phosphate whose average particle diameter was controlled to 1.1 μm, and copper-supported glass whose average particle diameter was controlled to the size described in the table ( Toho Gosei "NS-20C": The inorganic carrier for Toho Gosei "NS-20C" corresponds to aluminum silicate glass (0.28 g), and the mixture is stirred to obtain Composition 23. The obtained composition 23 of Example 23 contains an inorganic substance (1), a second metal-containing substance (two kinds of inorganic substances (2)), a silicate compound as a hydrophilic component, and a solvent.
Using the obtained composition 23, various evaluations were performed by the same method as the composition 8. The results are shown in Table 3.

Comparative Example 4: Preparation of Composition R4
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.
Various evaluation was implemented by the method similar to the composition 8 using composition R4 obtained. The results are shown in Table 3.

Comparative Example 5 Preparation of Composition R5
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.
Various evaluation was implemented by the method similar to the composition 8 using obtained composition R5. The results are shown in Table 3.

Comparative Example 6: Preparation of Composition R6
Example 7 is the same as Example 8, except that dispersant C is not used, and 0.1 g of a silicate compound ("MKC (registered trademark) Silicate" MS 51 "manufactured by Mitsubishi Chemical Corporation) and 200 g of pure water are used instead of dispersant C The composition R6 of Comparative Example 6 was prepared by the method of
Various evaluation was implemented by the method similar to the composition 8 using obtained composition R6. The results are shown in Table 3.

Comparative Example 7: Preparation of Composition R7
The same method as in Example 11 except that Dispersant D was not used, and 14 g of a silicate compound ("MKC (registered trademark) Silicate" MS 51 "manufactured by Mitsubishi Chemical Corp.) and 536 g of pure water were used instead of Dispersant D. Thus, composition R7 of Comparative Example 7 was prepared.
Various evaluation was implemented by the method similar to the composition 8 using obtained composition R7. The results are shown in Table 3.

"BHT" in the table is an abbreviation of dibutyl hydroxytoluene.
“Zirconium phosphate” in the table is “NS-10” manufactured by Toagosei Co., Ltd., whose average particle diameter 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 has an average particle diameter controlled to the size described in the table “Tosoh Synthetic“ NS-20C: Inorganic carrier of Toago Synthetic “NS-20C” is aluminum silicate glass Applicable ".

From the results of Table 3, it can be confirmed that the films obtained by the compositions of Examples 8 to 23 are excellent in antibacterial property and deodorizing property. In particular, it was confirmed that the deodorizing property lasts for a long time.
Further, from the comparison with Examples 8 to 14, all of the inorganic substance (1) and the second metal-containing substance are particles, and the average particle diameters of the inorganic substance (1) and the second metal-containing substance are all 0. When it is 6 micrometers or less (preferably 0.5 micrometers or less), it was confirmed that it is excellent by deodorizing property.
Further, from the comparison between Example 8 and Example 16 and Example 20, Example 15 and Example 17 and Example 21, when citric acid was used in combination as an additive, it was confirmed that the deodorizing property is superior.
Moreover, when contrast with Example 8 and Example 19, when 2 or more types of metal carrying | support carriers are used together as a 2nd metal containing material (Preferably, 2nd metal organic support and 2nd metal inorganic support are used together (In the case of (1)), it was confirmed that the deodorizing property is excellent.
Moreover, from the comparison of Example 15 and Example 22, when the inorganic substance (1) contains silver carrying glass and the second metal-containing substance contains copper carrying glass, it is confirmed that the deodorizing property is excellent.

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 compound ("MKC (registered trademark) Silicate" MS 51 "manufactured by Mitsubishi Chemical Corporation), 0.41 g of aluminum chelate D (aluminium bis (ethyl acetoacetate) mono ( Acetyl acetonate), Ethanol dilution: 1.3 g solid content concentration, 1.3 g, nonionic surfactant ("Emarex 715" manufactured by Nippon Emulsion Co., Ltd., pure water dilution: solid content concentration 0.5 mass%) After sequentially adding 3 g, 0.8 g of an anionic surfactant (“Rabisol A-90” manufactured by NOF Corporation, pure water dilution: solid content concentration 0.2 mass%), 2.7 g of isopropanol, an inorganic substance (1 ) (Silver-loaded glass whose average particle diameter is controlled to 1.1 μm (the average particle diameter of Bacterite MP-103DV manufactured by Fuji Chemical is controlled to 1.1 μm) In addition, the inorganic carrier of “Bacterite MP-103DV” manufactured by Fuji Chemical Co., Ltd. corresponds to phosphate glass), ethanol / water solvent dilution: solid content concentration 25.3 mass%) 0.039 g, Dispersing agent (BYK "DISPERBYK (registered trademark)-180") 0.04 g, ethanol 1.4 g, second metal-containing substance (average particle diameter is controlled to 3.1 μm copper-supported glass (Toagosei "NS" It corresponds to what controlled the average particle diameter of "-20C" to 3.1 micrometers. In addition, the inorganic carrier of "Tosoh Synthetic" NS-20C "corresponds to aluminum silicate glass.): Solid content concentration 100 mass%) 0.489 g was added and stirred for 20 minutes to obtain composition 24.
The obtained composition 24 of Example 24 contains an inorganic substance (1), a second metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.
Various evaluations were performed using the obtained composition 24 according to the following <Evaluation D>.
Incidentally, the following evaluation D was set to a more severe evaluation condition than the above-mentioned evaluations A to C.

<Evaluation D>
(Preparation of test sample)
The composition 24 obtained above was evaluated for its deodorizing property based on the test shown below.
First, a non-woven non-woven fabric was prepared, and the composition 24 was jetted to the non-woven fabric so that 0.06 g of the composition 24 adhered per 100 cm ^{2 of} non-woven fabric. Next, the obtained non-woven fabric with composition 24 was dried at 25 ° C. for 2 days to produce a film-coated substrate 24.

(Evaluation of deodorant)
The ammonia smelling urine was sprayed on the film-coated substrate 24 by 10 g and left at room temperature. The odor after 1 h and 8 h after sensory standing was evaluated sensoryily. The results are shown in Table 4.

«Evaluation criteria»
"AA": I feel only a faint odor.
"A": Almost no odor.
"B": A slight odor is felt.
"C": A slight odor is felt.
"D": I feel an odor.

(Evaluation of antibacterial activity)
The antimicrobial properties of the film-coated substrate 24 were evaluated.
The evaluation of the antimicrobial property was conducted in accordance with the evaluation method described in JIS Z 2801: 2012, using E. coli and changing the contact time to the bacterial solution to 24 hours to carry out the test. The antimicrobial 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 2.5 or more "B": antibacterial activity value 1.0 or more and less than 2.5 "C": antibacterial activity value 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 described 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 respectively prepared and evaluated in the same manner as in Examples 24 to 30 except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4. The results are shown in Table 4.

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

[Examples 52 to 58: Preparation of Compositions 52 to 58]
Compositions 52 to 58 were respectively 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 described in Table 4. The results are shown in Table 4.

[Examples 59 to 65: Preparation of Compositions 59 to 65]
Compositions 59 to 65 were respectively 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 described in Table 4. The results are shown in Table 4.

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

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

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

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

[Examples 101 to 107: Preparation of Compositions 101 to 107]
Compositions 101 to 102 were prepared in the same manner as in Examples 24 to 30, except that the type and content of the inorganic substance (1) and the average particle diameter of the second metal-containing material were changed to the types and content described in Table 4. 107 were each prepared and evaluated. The results are shown in Table 4.
In addition, the inorganic substance (1) used in Examples 101 to 107 has a silver-supported zeolite whose average particle diameter is controlled to 0.3 μm (“Zeol 4A” manufactured by Nakamura Cement Co., Ltd., water dilution: solid content concentration 19 mass%) It is.

Examples 108 to 114: Preparation of Compositions 108 to 114
The type and content of the inorganic substance (1) were changed to the type and content described in Table 4, and the content of the inorganic substance (2) and the average particle size were changed to the content and average particle size described in Table 4. Compositions 108-114 were prepared and evaluated as in Examples 24-30, respectively, except for the following. The results are shown in Table 4.
In addition, the inorganic substance (1) used in Examples 108 to 114 is a silver-supported zirconium phosphate ("Novalon AG300" manufactured by Toagosei Co., Ltd .; solid content concentration: 100% by mass) whose average particle diameter is controlled to 1.0 μm. .

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

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

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

[Examples 143 to 149: Preparation of Compositions 143 to 149]
Example except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4, and the type of the second metal-containing substance and the content thereof were adjusted to the amounts described in Table 4. Compositions 143-149 were prepared and evaluated as in 24-30, respectively. The results are shown in Table 4.
The second metal-containing material used in Examples 143 to 149 is a copper-supported polymer particle (corresponding to an organic material containing a second metal) whose average particle diameter is controlled to 0.6 μm.
The copper-supported polymer particles were produced and used by the following method.

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

In a container, 150 g of an aqueous dispersion (solid content concentration: 0.1% by mass) of polymer particles (Nippon Shokuhin “Epoler 100 W”, average particle diameter: 150 nm) is stirred while a silicate compound (MKC Corporation “MKC” 0.1 g of (registered trademark) Silicate MS 51 ") was added and stirred for 20 minutes. Subsequently, 50 g of copper oxide ("Copper oxide (II) COPPER OXIDE" manufactured by Kanto Chemical Co., Ltd.) aqueous dispersion (solid content concentration 0.01 mass%: average particle size 30 nm) whose particle size is controlled is added to this stirred product, The mixture was further stirred for 20 minutes to obtain a dispersion F.
Next, the obtained dispersion F was centrifuged to precipitate 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. According to observation with an optical microscope, the copper-supporting polymer particle has a structure in which copper oxide particles are supported on the surface of the polymer particle, and a silane is formed by condensation of a silicate compound in at least one region on the surface of the polymer particle. It confirmed that the film of the compound was formed. In addition, the copper carrying | support polymer particle produced two types of sizes, average particle diameter 0.6 micrometer, and average particle diameter 0.3 micrometer, by adjusting dispersion time.

Examples 150 to 156: Preparation of Compositions 150 to 156
Example except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4, and the type of the second metal-containing substance and the content thereof were adjusted to the amounts described in Table 4. Compositions 150-156 were prepared and evaluated as in 24-30, respectively. The results are shown in Table 4.
The second metal-containing material used in Examples 150 to 156 is a copper-supported polymer particle (corresponding to an organic material containing a second metal) whose average particle diameter is controlled to 0.3 μm.

Examples 157-163: Preparation of Compositions 157-163
Example except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4, and the type of the second metal-containing substance and the content thereof were adjusted to the amounts described in Table 4. Compositions 157-163 were prepared and evaluated as in 24-30, respectively. The results are shown in Table 4.
The second metal-containing material used in Examples 157 to 163 is a copper oxide particle (corresponding to the inorganic material (2)) whose average particle diameter is controlled to be 0.03 μm.

Examples 164 to 170: Preparation of Compositions 164 to 170
Example except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4, and the type of the second metal-containing substance and the content thereof were adjusted to the amounts described in Table 4. Compositions 164-170 were prepared and evaluated as in 24-30, respectively. The results are shown in Table 4.
The second metal-containing material used in Examples 164 to 170 is a copper-supported polymer particle (corresponding to an organic material containing a second metal) whose average particle diameter is controlled to 0.6 μm.

[Examples 171 to 177: Preparation of Compositions 171 to 177]
Example except that the average particle size of the inorganic substance (1) was adjusted to the size described in Table 4, and the type of the second metal-containing substance and the content thereof were adjusted to the amounts described in Table 4. Compositions 171-177 were prepared and evaluated as in 24-30, respectively. The results are shown in Table 4.
The second metal-containing substance used in Examples 171 to 177 is a copper-supported polymer particle (corresponding to an organic substance containing a second metal) whose average particle diameter is controlled to 0.3 μm.

Examples 178 to 184: Preparation of Compositions 178 to 184
Compositions 178 to 184 were respectively 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 described in Table 4. The results are shown in Table 4.

Examples 185 to 191 Preparation of Compositions 185 to 191
Compositions 185 to 191 were respectively 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 described in Table 4. The results are shown in Table 4.

[Examples 192 to 198: Preparation of Compositions 192 to 198]
Compositions 192 to 198 were respectively 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 described in Table 4. The results are shown in Table 4.

Examples 199 to 205: Preparation of Compositions 199 to 205
Compositions 199 to 205 were respectively 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 described in Table 4. The results are shown in Table 4.

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

[Examples 213 to 219: Preparation of Compositions 213 to 219]
Example 87 except that as the second metal-containing substance, zirconium phosphate (“NS-10” manufactured by Toagosei Co., Ltd.) whose average particle diameter was controlled to 0.8 μm was further added in the amount described in Table 4 Compositions 213-219 were respectively prepared and evaluated in the same manner as -93. The results are shown in Table 4.

Example 220 Preparation of Composition 220
The second metal inclusion 1 uses aluminum silicate (“NS-20” manufactured by Toagosei Co., Ltd.) whose average particle diameter is controlled to 0.15 μm, and the second metal inclusion 2 has an average particle diameter of 0.8 μm The composition 220 was prepared and evaluated in the same manner as in Example 219 except that 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 blended. 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 blended. 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 blended. 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 Example 40 except that the second metal-containing material was not blended. 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 blended. 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 blended. The results are shown in Table 4.

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

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

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

Comparative Examples 22 and 23 Preparation of Compositions R22 and R23
Compositions R22 and R23 were prepared and evaluated in the same manner as in Example 150 and Example 152, respectively, except that silver-supporting glass ("Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd.) was not blended. . The results are shown in Table 4.

[Comparative Examples 24 and 25: Preparation of Compositions R24 and R25]
The composition R24 and the composition R25 were respectively prepared and evaluated in the same manner as in Example 157 and Example 159 except that silver-supporting glass ("Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd.) was not blended. . 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-supporting glass ("Bacterite MP-103DV" manufactured by Fuji Chemical Co., Ltd.) and copper-supporting glass ("NS-20C" manufactured by Toagosei Co., Ltd.) were not blended. 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 (“NS-20” manufactured by Toagosei Co., Ltd., whose average particle size was controlled to the size described in the table, was blended instead of zirconium phosphate). 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 mass%)” manufactured by Fuji Chemical Co., Ltd., whose average particle diameter 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-supporting glass” is “NS-20C” (solid content: 100% by mass) manufactured by Toagosei Co., Ltd., whose average particle diameter is controlled to the size described in the table. The inorganic carrier "NS-20C" manufactured by Toagosei Co., Ltd. corresponds to aluminum silicate glass.
"Silver-loaded zeolite" in the table is "Zeool 4A" (solid content 19%) manufactured by Nakamura Cemented Carbide in which the average particle diameter is controlled to the size described in the table.
"Silver-supported zirconium phosphate" in the table is "Novalon AG300" (solid content: 100% by mass) manufactured by Toagosei Co., Ltd. whose average particle diameter is controlled to the size described in the table.
"Copper oxide" in the table is copper oxide (solid content: 100% by mass) whose average particle diameter 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., whose average particle diameter 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 diameter is controlled to the size described in the table.

From the results of Examples 24 to 100, it was confirmed that the deodorizing properties of the formed film are more excellent when the average particle diameter is 1.2 μm or less for both the silver-supporting glass and the copper-supporting glass.
Above all, according to the results of Examples 52 to 72, when the average particle diameter of one of silver-supporting glass and copper-supporting glass is 1.2 μm or less, and the other is 0.9 μm or less, It was confirmed that the deodorizing property of the formed film is more excellent. In addition, among the above, it is preferable that the average particle diameter of one of the silver-supporting glass and the copper-supporting glass is 1.2 μm or less and the other is 0.6 μm or less, It was confirmed that the deodorizing property of the formed film is more excellent when the average particle diameter is 0.9 μm or less for any of the copper-supporting glass.
In addition, in particular, according to the results of Examples 73 to 93, when any of the silver-supporting glass and the copper-supporting glass has an average particle diameter of 0.5 μm or less (preferably, any one of the silver-supporting glass and the copper-supporting glass It was confirmed that the deodorizing property of the formed film is more excellent) when the average particle diameter of is 0.5 μm or less and the other average particle diameter is 0.3 μm or less).
In addition, according to the results of Examples 94 to 100, when any of the silver-supporting glass and the copper-supporting glass has an average particle size of 0.3 μm or less, the deodorizing properties of the formed film tend to be more excellent. Was confirmed.

From the comparison of Examples 94 to 100 and Examples 101 to 107, it was confirmed that when the inorganic carrier of the inorganic substance (1) is glass, the deodorizing properties of the formed film are more excellent.

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

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

Also, from the comparison of Examples 94 to 100 and Examples 192 to 205, when the content of the dispersant in the composition is 15% by mass or more with respect to the total solid content of the composition (Example 192- It is confirmed that the deodorizing property of the formed film tends to be more excellent).

Also, from the comparison of Examples 178 to 191 and Examples 94 to 100, it was confirmed that when the composition contains a hydrophilic component, the deodorizing property and the antibacterial property of the formed film are more excellent.

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

In a container, 150 g of an aqueous dispersion (solid content concentration: 0.1% by mass) of polymer particles (Nippon Shokuhin “Epoler 100 W”, average particle diameter: 150 nm) is stirred while a silicate compound (MKC Corporation “MKC” 0.1 g of (registered trademark) Silicate MS 51 ") was added and stirred for 20 minutes. Subsequently, 50 g of copper oxide ("Copper oxide (II) COPPER OXIDE" manufactured by Kanto Chemical Co., Ltd.) aqueous dispersion (solid content concentration 0.01 mass%: average particle size 30 nm) whose particle size is controlled is added to this stirred product, The mixture was further stirred for 20 minutes to obtain a dispersion G.

Next, the obtained dispersion G was centrifuged to precipitate 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. According to observation with an optical microscope, the copper-supporting polymer particle has a structure in which copper oxide particles are supported on the surface of the polymer particle, and a silane is formed by condensation of a silicate compound in at least one region on the surface of the polymer particle. It confirmed that the film of the compound was formed.
In addition, the copper-supported polymer particles had an average particle size of 0.6 μm.

In the obtained dispersion liquid G, copper-supporting glass (“NS-20C” manufactured by Toagosei Co., Ltd.) as a first metal inorganic carrier: the inorganic carrier “NS-20C” manufactured by Toagosei Co., Ltd. corresponds to aluminum silicate glass. Reference composition 1 was obtained by adding and stirring 0.1 g.
The obtained Reference Composition 1 of Reference Example 1 includes a first metal organic carrier, a second metal inorganic carrier, a silicate compound as a hydrophilic component, and a solvent.

(Average particle diameter of first metal inorganic carrier, first metal organic carrier)
The average particle diameter 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.

Reference Composition 1 of Reference Example 1 obtained was evaluated in the same manner as in Example 1. 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.
Reference Composition 1 of Reference Example 1 obtained was evaluated in the same manner as in Example 1. The results are shown in Table 5.

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

Claims

An inorganic substance 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;
A composition containing a solvent.
Metal-supported inorganic substance comprising an inorganic substance containing the first metal, the first metal alone, an oxide of the first metal, and an inorganic support and the first metal supported on the inorganic support The composition according to claim 1, which is at least one selected from the group consisting of a carrier.
A metal-supported inorganic substance comprising an inorganic substance containing the second metal, the single substance of the second metal, an oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support. The composition according to claim 1, which is at least one selected from the group consisting of a carrier.
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 average particle of either the inorganic substance containing the first metal and the inorganic substance containing the second metal is a particle, and the inorganic substance containing the first metal and the inorganic substance containing the second metal The average diameter of the particles is 1.2 μm or less, and the average particle diameter of the other is 0.6 μm or less, or the average of any of the first metal-containing inorganic substance and the second metal-containing inorganic substance The composition according to claim 4, wherein the particle size is 0.9 μm or less.
The composition according to any one of the preceding claims, wherein the first metal is silver and the second metal is copper.
7. The silver-supported inorganic carrier according to claim 1, wherein the inorganic substance containing the first metal is a silver-supported inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier. Composition as described.
8. The copper-supported inorganic carrier according to any one of claims 1 to 7, wherein the inorganic substance containing the second metal is a copper-supported inorganic carrier having a second inorganic carrier and copper supported on the second inorganic carrier. Composition as described.
The composition according to claim 7, wherein the first inorganic carrier is glass.
9. The composition of claim 8, wherein the second inorganic carrier is glass.
The inorganic substance containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic substance 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-loaded glass having copper.
The composition according to any one of claims 1 to 11, further comprising 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 substance containing a first metal;
An inorganic substance containing a second metal different from the first metal, and a component containing at least one second metal selected from the group consisting of an organic substance containing the second metal Do the membrane.
Metal-supported inorganic substance comprising an inorganic substance containing the first metal, the first metal alone, an oxide of the first metal, and an inorganic support and the first metal supported on the inorganic support The membrane according to claim 14, which is at least one selected from the group consisting of a carrier.
A metal-supported inorganic substance comprising an inorganic substance containing the second metal, the single substance of the second metal, an oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support. The membrane according to claim 14, which is at least one selected from the group consisting of a carrier.
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 average particle of either the inorganic substance containing the first metal and the inorganic substance containing the second metal is a particle, and the inorganic substance containing the first metal and the inorganic substance containing the second metal The average diameter of the particles is 1.2 μm or less, and the average particle diameter of the other is 0.6 μm or less, or the average of any of the first metal-containing inorganic substance and the second metal-containing inorganic substance 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.
20. The silver-supported inorganic carrier according to any one of claims 14 to 19, wherein the inorganic substance containing the first metal is a silver-supported inorganic carrier having a first inorganic carrier and silver supported on the first inorganic carrier. Membrane described.
21. The copper-supported inorganic support according to any one of claims 14 to 20, wherein the inorganic substance containing the second metal is a copper-supported inorganic support having a second inorganic support and copper supported on the second inorganic support. Membrane described.
21. The membrane of claim 20, wherein the first inorganic support is glass.
22. A membrane according to claim 21, wherein the second inorganic support is glass.
The inorganic substance containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic substance 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-loaded glass having copper.
The membrane according to any one of claims 14 to 24, further comprising a hydrophilic binder.
26. The hydrophilic polymer according to claim 25, wherein the hydrophilic binder is at least one selected from the group consisting of a hydrolyzate of a compound having a hydrolyzable group bonded to a silicon atom, and a hydrolytic condensate thereof, or a hydrophilic polymer. Membrane described.
A membrane-coated substrate comprising a substrate and the membrane according to any one of claims 14 to 26.
Applying the composition according to any one of claims 1 to 13 containing a hydrophilic binder precursor on the surface of a substrate to form a composition layer;
Curing the composition layer to obtain a film.
A method for producing a membrane-coated substrate, 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, a first metal-containing inorganic substance disposed on or within the base material, and a second metal-containing inorganic substance different from the first metal and the second metal A modified substrate comprising: at least one second metal-containing component selected from the group consisting of metal-containing organic substances.
A base material, a first metal-containing inorganic substance disposed on or within the base material, and a second metal-containing inorganic substance different from the first metal and the second metal A modified substrate comprising a component containing at least one second metal selected from the group consisting of metal-containing organic substances, and a hydrophilic binder.
Metal-supported inorganic substance comprising an inorganic substance containing the first metal, the first metal alone, an oxide of the first metal, and an inorganic support and the first metal supported on the inorganic support The modified substrate according to claim 30 or 31, which is at least one selected from the group consisting of a carrier.
A metal-supported inorganic substance comprising an inorganic substance containing the second metal, the single substance of the second metal, an oxide of the second metal, and an inorganic support and the second metal supported on the inorganic support. The modified substrate according to claim 30 or 31, which is at least one selected from the group consisting of a carrier.
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 average particle of either the inorganic substance containing the first metal and the inorganic substance containing the second metal is a particle, and the inorganic substance containing the first metal and the inorganic substance containing the second metal The average diameter of the particles is 1.2 μm or less, and the average particle diameter of the other is 0.6 μm or less, or the average of any of the first metal-containing inorganic substance and the second metal-containing inorganic substance 35. The modified substrate of claim 34, wherein the particle size is 0.9 μm or less.
The modified substrate according to any of claims 30 to 35, wherein the first metal is silver and the second metal is copper.
37. The silver-supported inorganic support according to any one of claims 30 to 36, wherein the inorganic substance containing the first metal is a silver-supported inorganic support having a first inorganic support and silver supported on the first inorganic support. Modified substrate as described.
38. The copper-supported inorganic support according to any one of claims 30 to 37, wherein the inorganic substance containing the second metal is a copper-supported inorganic support having a second inorganic support and copper supported on the second inorganic support. Modified substrate as described.
39. The modified substrate of claim 37, wherein the first inorganic support is glass.
39. The modified substrate of claim 38, wherein the second inorganic support is glass.
The inorganic substance containing the first metal is a silver-supported glass having glass and silver supported on the glass, and the inorganic substance containing the second metal is supported on the glass and the glass The modified substrate according to any one of claims 34 to 36, which is a copper-loaded glass having copper supported thereon.