CN110809405A

CN110809405A - Composition, film-attached substrate, method for producing film-attached substrate, and modified substrate

Info

Publication number: CN110809405A
Application number: CN201880039420.7A
Authority: CN
Inventors: 三井哲朗
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2017-07-10
Filing date: 2018-07-10
Publication date: 2020-02-18
Also published as: WO2019013227A1; JPWO2019013227A1

Abstract

The invention provides a composition capable of forming a film and a modified substrate having excellent antibacterial property and excellent deodorization property. Another object of the present invention is to provide a film, a film-attached substrate, a method for producing a film-attached substrate, and a modified substrate. The composition of the present invention comprises: inorganic substances containing a 1 st metal; at least 1 metal-2-containing component selected from the group consisting of an inorganic material containing a metal-2 different from the metal-1 and an organic material containing the metal-2; and a solvent.

Description

Composition, film-attached substrate, method for producing film-attached substrate, and modified substrate

Technical Field

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

Background

An antibacterial film containing antibacterial agent particles and a binder is known. The antibacterial film has a function of inhibiting the proliferation of bacteria on the surface thereof.

For example, patent document 1 describes "an antibacterial coating composition comprising 1) glass particles, ceramic particles or porous silica gel particles each containing metal ions having an antibacterial action; and 2) organosilane capable of undergoing hydrolysis and polycondensation or a partial hydrolysate thereof as a main component. ".

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 8-027404

Disclosure of Invention

Technical problem to be solved by the invention

The present inventors have made studies to produce an antibacterial film formed using the antibacterial coating composition described in patent document 1, and have found that the deodorizing performance does not satisfy the current level of requirements.

Accordingly, an object of the present invention is to provide a composition capable of forming a film or a modified substrate having excellent antibacterial properties and excellent deodorizing properties.

Further, another object of the present invention is to provide a film, a film-attached substrate, a method for producing a film-attached substrate, and a modified substrate.

Means for solving the technical problem

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the problems can be solved by the following configurations.

[ 1] A composition comprising: inorganic substances containing a 1 st metal;

at least 1 metal-2-containing component selected from the group consisting of an inorganic material containing a metal-2 different from the metal-1 and an organic material containing the metal-2; and

a solvent.

The composition according to [ 1], wherein the inorganic material containing the 1 st metal is at least 1 selected from the group consisting of a simple substance of the 1 st metal, an oxide of the 1 st metal, and a metal-supporting inorganic carrier having an inorganic carrier and the 1 st metal supported on the inorganic carrier.

The composition according to [ 1], wherein the inorganic material containing the 2 nd metal is at least 1 selected from the group consisting of a simple substance of the 2 nd metal, an oxide of the 2 nd metal, and a metal-supporting inorganic carrier having an inorganic carrier and the 2 nd metal supported on the inorganic carrier.

The composition according to any one of [ 1] to [ 3 ], wherein the component containing the 2 nd metal is an inorganic substance containing the 2 nd metal.

The composition according to [ 5 ] or [ 4 ], wherein the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal are particles, and either one of the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal has an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, or both the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal have an average particle size of 0.9 μm or less.

The composition according to any one of [ 1] to [ 5 ], wherein the 1 st metal is silver and the 2 nd metal is copper.

The composition according to any one of [ 1] to [ 6 ], wherein the inorganic substance containing the 1 st metal is a silver-carrying inorganic carrier having a 1 st inorganic carrier and silver carried on the 1 st inorganic carrier.

The composition according to any one of [ 1] to [ 7 ], wherein the inorganic substance containing the 2 nd metal is a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier.

The composition according to [ 7 ], wherein the 1 st inorganic carrier is glass.

[ 10 ] the composition according to [ 8 ], wherein the 2 nd inorganic carrier is glass.

The composition according to any one of [ 4 ] to [ 6 ], wherein the inorganic substance containing the 1 st metal is a silver-loaded glass having glass and silver loaded on the glass, and the inorganic substance containing the 2 nd metal is a copper-loaded glass having glass and copper loaded on the glass.

The composition according to any one of [ 1] to [ 11 ], further comprising a hydrophilic component selected from the group consisting of a hydrophilic adhesive precursor and a hydrophilic adhesive.

The composition according to [ 12 ], wherein the hydrophilic component contains at least 1 selected from the group consisting of a silicate compound, a monomer having a hydrophilic group and a polymer having a hydrophilic group.

[ 14 ] A film comprising: inorganic substances containing a 1 st metal; and

at least 1 component containing the 2 nd metal selected from the group consisting of an inorganic substance containing the 2 nd metal different from the 1 st metal and an organic substance containing the 2 nd metal.

The membrane according to [ 14 ], wherein the inorganic material containing the 1 st metal is at least 1 selected from the group consisting of a simple substance of the 1 st metal, an oxide of the 1 st metal, and a metal-supporting inorganic carrier having an inorganic carrier and the 1 st metal supported on the inorganic carrier.

The membrane according to [ 14 ], wherein the inorganic substance containing the 2 nd metal is at least 1 selected from the group consisting of a simple substance of the 2 nd metal, an oxide of the 2 nd metal, and a metal-supporting inorganic carrier having an inorganic carrier and the 2 nd metal supported on the inorganic carrier.

[ 17 ] the film according to any one of [ 14 ] to [ 16 ], wherein the component containing the 2 nd metal is an inorganic substance containing the 2 nd metal.

[ 18 ] the film according to [ 17 ], wherein the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal are particles, one of the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal has an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, or both of the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal have an average particle size of 0.9 μm or less.

[ 19 ] the film according to any one of [ 14 ] to [ 18 ], wherein the 1 st metal is silver and the 2 nd metal is copper.

A film according to any one of [ 14 ] to [ 19 ], wherein the inorganic substance containing the 1 st metal is a silver-carrying inorganic carrier having a 1 st inorganic carrier and silver carried on the 1 st inorganic carrier.

[ 21] the film according to any one of [ 14 ] to [ 20 ], wherein the inorganic substance containing the 2 nd metal is a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier.

[ 22 ] the film according to [ 20 ], wherein the 1 st inorganic carrier is glass.

[ 23 ] the film according to [ 21], wherein the 2 nd inorganic carrier is glass.

[ 24 ] the film according to any one of [ 17 ] to [ 19 ], wherein the inorganic substance containing the 1 st metal is a silver-carrying glass having glass and silver carried on the glass, and the inorganic substance containing the 2 nd metal is a copper-carrying glass having glass and copper carried on the glass.

[ 25 ] the film according to any one of [ 14 ] to [ 24 ], further comprising a hydrophilic binder.

The film according to [ 25 ], wherein the hydrophilic binder is at least 1 selected from the group consisting of a hydrolysate of a compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis-condensation product thereof, and a hydrophilic polymer.

A film-coated substrate comprising a substrate and the film according to any one of [ 14 ] to [ 26 ].

[ 28 ] A method for producing a film-attached substrate, comprising: a step of applying the composition according to any one of [ 1] to [ 13 ] containing a hydrophilic adhesive precursor to the surface of a substrate to form a composition layer; and

and curing the composition layer to obtain a film.

A method for producing a film-coated substrate, which comprises the step of applying a composition comprising any one of the hydrophilic adhesives [ 1] to [ 13 ] to the surface of a substrate to form a film.

[ 30 ] A modified substrate comprising a substrate, an inorganic substance containing a 1 st metal disposed on or in the substrate, and at least 1 component containing a 2 nd metal selected from the group consisting of an inorganic substance containing a 2 nd metal different from the 1 st metal and an organic substance containing the 2 nd metal.

[ 31 ] A modified substrate comprising a substrate, an inorganic substance containing a 1 st metal and disposed on or in the substrate, at least 1 metal-containing component selected from the group consisting of an inorganic substance containing a 2 nd metal different from the 1 st metal and an organic substance containing the 2 nd metal, and a hydrophilic adhesive.

The modified substrate according to [ 30 ] or [ 31 ], wherein the inorganic substance containing the 1 st metal is at least 1 selected from the group consisting of a simple substance of the 1 st metal, an oxide of the 1 st metal, and a metal-supporting inorganic carrier having an inorganic carrier and the 1 st metal supported on the inorganic carrier.

The modified substrate according to [ 30 ] or [ 31 ], wherein the inorganic substance containing the 2 nd metal is at least 1 selected from the group consisting of a simple substance of the 2 nd metal, an oxide of the 2 nd metal, and a metal-supporting inorganic carrier having an inorganic carrier and the 2 nd metal supported on the inorganic carrier.

The modified substrate according to any one of [ 30 ] to [ 33 ], wherein the component containing the 2 nd metal is an inorganic substance containing the 2 nd metal.

The modified substrate according to [ 34 ], wherein the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal are particles, one of the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal has an average particle diameter of 1.2 μm or less and the other has an average particle diameter of 0.6 μm or less, or both of the inorganic substance containing the 1 st metal and the inorganic substance containing the 2 nd metal have an average particle diameter of 0.9 μm or less.

The modified substrate according to any one of [ 30 ] to [ 35 ], wherein the 1 st metal is silver and the 2 nd metal is copper.

The modified substrate according to any one of [ 30 ] to [ 36 ], wherein the inorganic substance containing the 1 st metal is a silver-carrying inorganic carrier having a 1 st inorganic carrier and silver carried on the 1 st inorganic carrier.

The modified substrate according to any one of [ 30 ] to [ 37 ], wherein the inorganic substance containing the 2 nd metal is a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier.

The modified substrate according to [ 37 ], wherein the 1 st inorganic carrier is glass.

[ 40 ] the modified substrate according to [ 38 ], wherein the 2 nd inorganic carrier is glass.

The modified substrate according to any one of [ 34 ] to [ 36 ], wherein the inorganic substance containing the 1 st metal is a silver-loaded glass having glass and silver loaded on the glass, and the inorganic substance containing the 2 nd metal is a copper-loaded glass having glass and copper loaded on the glass.

Effects of the invention

According to the present invention, a composition capable of forming a film or a modified substrate having excellent antibacterial properties and excellent deodorizing properties can be provided. Further, the present invention can provide a film, a film-attached substrate, a method for producing a film-attached substrate, and a modified substrate.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be made in accordance with exemplary embodiments of the present invention, but the present invention is not limited to these embodiments.

In the labeling of a group (atomic group) in the present specification, a substituted or unsubstituted label is not described to include a group having no substituent and a group having a substituent, as long as the effect of the present invention is not impaired. For example, "alkyl" means an alkyl group containing not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). The meaning is also the same for each compound.

In the present specification, "(meth) acrylate" represents both or either of acrylate and methacrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acryloyl" represents both or either of acryloyl and methacryloyl.

In the present specification, the numerical range represented by "to" means a range including numerical values described before and after "to" as a lower limit value and an upper limit value.

[ composition ]

The above composition (hereinafter, also referred to as "composition according to the embodiment") contains: an inorganic material containing a 1 st metal (hereinafter, also referred to as "inorganic material (1)" or "1 st metal-containing material"), a component containing at least 12 nd metal (hereinafter, also referred to as "2 nd metal-containing material") selected from the group consisting of an inorganic material containing a 2 nd metal different from the 1 st metal (hereinafter, also referred to as "inorganic material (2)") and an organic material containing the 2 nd metal, and a solvent.

In the present specification, the term "metal" includes a metal monomer (metal monomer particle), a metal ion, and a metal atom contained in a compound.

The film or the modified substrate formed from the composition has excellent antibacterial properties and deodorizing properties by containing the inorganic substance (1) and the 2 nd metal-containing substance.

As will be described later, when at least one of the metal-containing substance 2 selected from the group consisting of the inorganic substance 1 and the inorganic substance 2 is in the form of particles and has an average particle diameter of 1.2 μm or less, a film or a modified substrate having more excellent antibacterial properties and more excellent deodorizing properties can be obtained.

Among them, as described later, in the case where the inorganic substance (1) is a silver-carrying inorganic carrier having a 1 st inorganic carrier and silver carried on the 1 st inorganic carrier, and the inorganic substance (2) is a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier, a film or a modified substrate having more excellent antibacterial properties and more excellent deodorizing properties can be obtained. For example, it is presumed that in the urine odor generating means, urea is decomposed by enzymes generated by bacteria to become an ammonia source, but copper exhibits excellent enzymatic decomposition energy, thereby exhibiting high deodorizing ability. On the other hand, silver is known to exhibit high antibacterial properties. Therefore, it is presumed that when the film or the modified substrate includes the silver-carrying inorganic carrier and the copper-carrying inorganic carrier, more excellent antibacterial properties and more excellent deodorizing properties are exhibited. Further, copper exhibits not only high deodorizing ability as described above but also high antibacterial property, but the present inventors have speculated from various studies that silver and copper exhibit antibacterial property by different mechanisms from each other. As a result, it is considered that when the film or the modified substrate contains the silver-carrying inorganic carrier and the copper-carrying inorganic carrier, 2 respective antibacterial mechanisms based on copper and silver act on bacteria at the same time, and thus remarkably superior antibacterial properties can be obtained as compared with the case where each of them is used alone.

Further, in the case where the inorganic carrier of at least one of the silver-carrying inorganic carrier and the copper-carrying inorganic carrier (preferably, a copper-carrying inorganic carrier, and more preferably, a silver-carrying inorganic carrier and a copper-carrying inorganic carrier) is amorphous (amorphous), metal ions are more easily released from the 1 st metal and the 2 nd metal, and therefore the above-mentioned effects are further excellent.

The use of the composition is not particularly limited, and for example, the composition can be applied to diapers used in nursing places and exhibits excellent antibacterial and deodorant effects against urine odor.

Urine odor is caused by substances such as ammonia and trimethylamine contained in urine. When the urine absorbed by the diaper is left for a long time, the odor of the urine becomes stronger because the above-mentioned substances, which are the cause of the urine odor, further increase due to the action of bacteria.

On the other hand, when the film formed from the composition is formed on a portion of the diaper where urine and feces come into contact with the film, the increase of the substances such as ammonia and trimethylamine is suppressed because the proliferation of bacteria and the enzymatic decomposition of urine and feces substances by the bacteria are suppressed. Namely, the increase in odor is suppressed. Further, the deodorizing effect is stably maintained for a long period of time from the time when the diaper absorbs urine.

The above effects can be similarly obtained by a modified substrate described later formed using the above composition.

Hereinafter, each component contained in the above composition will be described in detail.

< inorganic substance (1) >

The inorganic substance (1) is not particularly limited, preferably, the antibacterial activity against escherichia (e.g., escherichia coli, etc.), staphylococcus (e.g., staphylococcus aureus (s.aureus), etc.), klebsiella (e.g., klebsiella oxytoca (k.oxytoca), klebsiella pneumoniae (k.pneumoniae), etc.), serratia marcescens (e.g., serratia marcescens (s.marcocens)), citrobacter (e.g., citrobacter freundii (c.freundii), citrobacter cruzi (c.diversus), etc.), enterobacter (e.g., enterobacter aerogenes (e.aerogenes), enterobacter cloacae (e.cloacae)), proteus (e.g., proteus mirabilis (p.mirabilis), proteus vulgaris (p.vulgarris), etc.), pseudomonas aeruginosa (e.g., pseudomonas aeruginosa, etc.), and morganella (e.g., morganella, etc.), and the like, including morganella (m.m.g., and/or the like.

The inorganic substance (1) may be a solid substance or a liquid substance, but from the viewpoint of further improving the effect of the present invention, the inorganic substance (1) is preferably a solid substance, and more preferably a particle (a particle existing as a particle in the composition).

The inorganic substance (1) contains a metal of No. 1. The form of the inorganic substance (1) is not particularly limited, and may be any of a simple substance of the 1 st metal (metal monomer particles), an ion of the 1 st metal, and an inorganic compound containing the 1 st metal (the compound is defined as a pure substance of a monomer that can be decomposed into 2 or more elements according to chemical changes), or a mixture thereof. The inorganic material (1) may be a composite of an inorganic compound and a 1 st metal. Examples of the composite include a metal-loaded carrier (hereinafter, also referred to as "metal-loaded inorganic carrier 1") having an inorganic carrier and a metal 1 (which may be, for example, any of a simple substance of the metal 1 (metal monomer particles), an ion of the metal 1, and a metal 1-containing compound (specifically, an inorganic compound containing the metal 1) supported on the inorganic carrier).

Among these, from the viewpoint of more excellent effects of the present invention, the inorganic substance (1) is preferably at least 1 selected from the group consisting of the simple substance (particle) of the 1 st metal, the ion of the 1 st metal, the oxide of the 1 st metal, and the 1 st metal-supporting inorganic carrier, more preferably at least 1 selected from the group consisting of the simple substance (particle) of the 1 st metal, the oxide of the 1 st metal, and the 1 st metal-supporting inorganic carrier, and further preferably the 1 st metal-supporting inorganic carrier.

The metal 1 is not particularly limited, and examples thereof include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel, and the like, and among them, silver, copper, zinc, aluminum, or zirconium is preferable, silver, copper, zinc, or aluminum is more preferable, silver or copper is further preferable, and silver is particularly preferable.

Examples of the inorganic substance (1) include an oxide, nitride, halide, cyanide, selenide, sulfide, telluride of the 1 st metal, and a salt of the 1 st metal.

Examples of the salt of the metal 1 include arsenate, hydrogen fluoride, bromate, chlorate, chromate, cyanate, hexafluoroantimonate, hexafluoroarsenate, hexafluorophosphate, iodate, isothiocyanate, molybdate, nitrate, nitrite, perchlorate, permanganate, perrhenate, phosphate, selenate, selenite, sulfate, sulfite, tetrafluoroborate, tetratungstate, thiocyanate, and vanadate.

The type of the inorganic carrier on which the 1 st metal inorganic carrier is supported is not particularly limited, and examples thereof include zinc calcium phosphate, zirconium phosphate, aluminum phosphate, calcium silicate, activated alumina, silica, silicate glass, borosilicate glass, phosphate glass, zeolite (crystalline aluminosilicate), apatite, hydroxyapatite, titanium phosphate, potassium titanate, hydrous bismuth oxide, hydrous zirconium oxide, and hydrotalcite; activated carbon; a metal; and the like.

In the present specification, the inorganic carrier on which the 1 st metal inorganic carrier is supported may be referred to as "1 st inorganic carrier".

The inorganic carrier may be crystalline or amorphous (amorphous), preferably amorphous, and more preferably glass. Examples of the material that can constitute the glass include silicates, borosilicates, phosphates, and the like, and among them, silicates are preferable, and aluminum silicates are more preferable.

The aluminum silicate can be natural or synthetic. As the aluminum silicate, a compound represented by the following formula (a) is preferable.

Al₂O₃·nSiO₂·mH₂O (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. Wherein n is preferably 8 to 15, and m is preferably 3 to 15.

As the inorganic material (1), inorganic materials (for example, zirconium phosphate, aluminum silicate, and the like) containing silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel, and the like can also be used in the inorganic carrier.

The metal-supported 1 st inorganic carrier is preferably a metal-supported zeolite, a metal-supported apatite, a metal-supported glass, a metal-supported zirconium phosphate or a metal-supported calcium silicate, which supports the 1 st metal, and more preferably a metal-supported glass.

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 is usually 0.01 μm or more, preferably 0.2 μm or more. The upper limit is not particularly limited, and examples thereof include 10 μm or less, preferably 5.0 μm or less. Among these, it is preferably 3.0 μm or less, more preferably 1.5 μm or less, further preferably 1.2 μm or less, further preferably 0.9 μm or less, particularly preferably 0.6 μm or less, most preferably 0.5 μm or less, and most preferably 0.3 μm or less.

In addition, when considering the precipitability and the transparency of the composition, the dispersion is improved by making the average particle size of the inorganic substance (1) small, and as a result, the transparency of the composition tends to be improved. From the viewpoint of more excellent transparency of the composition, the average particle diameter of the inorganic substance (1) is preferably 0.5 μm or less, more preferably 0.4 μm or less.

The average particle diameter of the particles of the inorganic substance (1) can be measured by observation with an electron microscope. Specifically, the average particle diameter is as follows: the particle diameter of the inorganic material (1) was measured from an electron microscope image for primary particles and secondary particles (the term "secondary particles" is defined as aggregates formed by fusing or contacting primary particles), and the average value was obtained by averaging the diameters of particles in a range of 90% of all the particles except for 5% of the particles on the side having the smallest diameter and 5% of the particles on the side having the largest diameter. That is, the average particle size is a value obtained from the primary particles and the secondary particles. And, the diameter refers to the circumscribed circle equivalent diameter of the particle.

When there is no large difference in particle shape of the particles of the inorganic substance (1), the average of the 3-order measurement values can be substituted by the average particle diameter by measuring the 3-order 50% volume cumulative diameter (D50) using a laser diffraction/scattering particle size distribution measuring apparatus manufactured by HORIBA, ltd.

When the average particle diameter of the inorganic substance (1) is within the above numerical range, the inorganic substance (1) is easily immobilized in a state of being exposed from the hydrophilic binder in a film or a modified substrate formed from the composition containing the hydrophilic binder, which will be described later. Therefore, for example, in the case where the inorganic substance (1) is a metal-supporting carrier, the metal is more easily released from the carrier, whereby the effect of the present invention is more excellent.

The method for forming the inorganic substance (1) may be any of a decomposition method (for example, a pulverization method) and a lamination method.

Examples of the method for pulverizing the inorganic substance (1) include dry pulverization and wet pulverization. For the dry pulverization, for example, a mortar, a jet mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, a bead mill, or the like can be suitably used. In addition, for the wet pulverization, various ball mills, high-speed rotary pulverizers, jet mills, bead mills, ultrasonic homogenizers, high-pressure homogenizers, and the like can be suitably used. For example, in a bead mill, the average particle diameter can be controlled by adjusting the diameter, type, amount of beads to be mixed, and the like.

The lamination method is a method in which raw material components such as hydroxide and organic metal are mixed with arbitrary components and reacted to directly form the inorganic substance (1).

The stacking method may be a batch method in which the raw material components are added to a vessel and stirred and mixed, or a method in which the raw material components are continuously mixed in a flow path and reacted (for example, a micro-reactor or double-tube mixing method), but the latter method is preferable.

The inorganic substance (1) may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the inorganic substance (1) (the total content of a plurality of inorganic substances (1) when included) in the composition is not particularly limited, but is preferably 0.001 to 55% by mass, more preferably 0.001 to 50% by mass, and still more preferably 0.01 to 40% by mass, based on the total solid content of the composition.

The content of the metal in the inorganic substance (1) is not particularly limited, and for example, in the case where the inorganic substance (1) is a metal-supporting carrier, the content of the metal is preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the metal-supporting carrier. When the composition contains a plurality of inorganic materials (1), the total content of the metals is preferably within the above numerical range.

< 2 nd Metal content >

The composition contains at least 1 kind (2 nd metal-containing substance) selected from the group consisting of an inorganic substance (2) and a 2 nd metal-containing organic substance.

The content of the 2 nd metal-containing material in the composition is not particularly limited, but is preferably 0.01 to 50% by mass, more preferably 0.01 to 40% by mass, still more preferably 0.1 to 35% by mass, yet more preferably 0.1 to 30% by mass, and particularly preferably 0.1 to 10% by mass.

The metal-containing compound (2) may be used alone in 1 kind or in combination of 2 or more kinds. When 2 or more kinds of the 2 nd metal-containing materials are used simultaneously, the total content is preferably within the above range.

The 2 nd metal is different from the 1 st metal. Wherein "different" indicates that the kind of the metal element is different.

The metal 2 is not particularly limited, and examples thereof include silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel, and the like, with silver, copper, zinc, aluminum, or zirconium being preferred, silver, copper, zinc, or aluminum being more preferred, and copper being even more preferred.

The form of the inorganic substance (2) is not particularly limited, and may be any of the simple substance (particles) of the 2 nd metal, ions of the 2 nd metal, or inorganic compounds containing the 2 nd metal, or may be a mixture thereof. The inorganic substance (2) may be a composite of an inorganic compound and a metal 2. Examples of the composite include a metal-supporting carrier (hereinafter, also referred to as "metal-supporting inorganic carrier") having an inorganic carrier and a metal 2 (which may be any of a simple substance of the metal 2 (metal monomer particles), an ion of the metal 2, and a compound containing the metal 2 (specifically, an inorganic compound containing the metal 2) supported on the inorganic carrier).

From the viewpoint of more excellent effects of the present invention, the inorganic substance (2) is more preferably at least 1 selected from the group consisting of a simple substance (particle) of the 2 nd metal, an oxide of the 2 nd metal, and a 2 nd metal-supporting inorganic carrier, and further preferably a 2 nd metal-supporting inorganic carrier.

As the inorganic support carrying the 2 nd metallic inorganic support, the same inorganic support as described as the inorganic support carrying the 1 st metallic inorganic support can be used. In the present specification, the inorganic carrier on which the 2 nd metallic inorganic carrier is supported may be referred to as "2 nd inorganic carrier".

Specific examples of the metal 2 inorganic carrier include metal-supported zeolite supporting metal 2, metal-supported apatite, metal-supported glass, metal-supported zirconium phosphate, and metal-supported calcium silicate, and metal-supported glass is more preferable.

As the inorganic material (2), inorganic materials (for example, zirconium phosphate, aluminum silicate, and the like) containing silver, copper, zinc, mercury, iron, lead, bismuth, titanium, tin, zirconium, aluminum, nickel, and the like can be used as the inorganic carrier.

Examples of the organic material containing the 2 nd metal include salts of the 2 nd metal. Examples of the salt of the metal 2 include acetate, acetylacetonate, acetylene metal, (cis, cis-1, 5-cyclooctadiene) -1,1,1,5,5, 5-hexafluoroacetylacetonate, diethyldithiocarbamate, 7-dimethyl-1, 1,1,2,2,3, 3-heptafluoro-4, 6-octanedionate, lactate, oxalate, perfluorobutyrate, perfluoropropionate, picrate, propionate, sulfadiazine, p-toluenesulfonate, trifluoromethanesulfonate, and trifluoroacetate.

The organic material containing the 2 nd metal may be a composite of an organic compound and the 2 nd metal. As the composite, for example, a metal-carrying support having an organic support and a metal-carrying 2 nd metal (which may be any of a simple substance of the 2 nd metal (metal monomer particles), an ion of the 2 nd metal, and a compound containing the 2 nd metal (as a compound containing the 2 nd metal, specifically, an inorganic compound containing the 2 nd metal) carried on the organic support, or an organic-inorganic composite including an inorganic compound containing the 2 nd metal and an organic compound disposed so as to cover the inorganic compound is preferable, and among them, a metal-carrying organic support having an organic support and a metal-carrying 2 nd metal carried on an organic support (hereinafter, also referred to as "metal-carrying 2 organic support") is more preferable.

Examples of the organic vehicle carrying the 2 nd metal organic vehicle include polymer particles.

Specific examples of the metal-organic carrier 2 include polymer particles (hereinafter, also referred to as "copper-carrying polymer") carrying a metal 2 selected from the group consisting of copper particles and copper oxide particles.

From the viewpoint of further improving the effects of the present invention, the average particle diameter of the copper particles and the copper oxide particles is preferably 90nm or less, more preferably 70nm or less, and still more preferably 50nm or less. The lower limit is not particularly limited, and is, for example, 1nm or more.

The average particle diameter of the copper particles and the copper oxide particles can be measured by the method for measuring the average particle diameter of the particles of the inorganic substance (1) described above.

In addition, when there is no significant change in particle shape between the copper particles or the copper oxide particles in the copper-carrying polymer particles and the state in which only the copper particles or the copper oxide particles are dispersed, the measured value based on the dynamic light scattering of the dispersion liquid using only the copper particles or the copper oxide particles may be substituted by the average particle diameter. In this case, the average particle diameter can be measured by dynamic light scattering using a particle size distribution measuring instrument based on laser diffraction or the like.

In the copper-carrying 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, 1nm or more. From the viewpoint of further improving the effect of the present invention, the average primary particle diameter of the copper particles and the copper oxide particles is more preferably 5 to 90nm, and still more preferably 5 to 50 nm.

In addition, "average primary particle diameter" means the following value: the diameter of each primary particle was measured from an image of an electron microscope, and the average value of the diameters of the primary particles in a range of 90% out of all the primary particles except for 5% of the primary particle number on the side where the diameter is the smallest and 5% of the primary particle number on the side where the diameter is the largest was obtained. Wherein the diameter represents a circumscribed circle equivalent diameter of the primary particle.

In the copper-carrying polymer particles, the average particle diameter of the polymer particles is preferably 100 to 1000nm, more preferably 100 to 800 nm.

The average particle diameter of the polymer particles can be measured by the method for 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, a polyurethane resin, (meth) acrylic resin, polystyrene- (meth) acrylic copolymer resin, or polyolefin resin is preferable. Examples of the polymer particles include NIPPON SHOKUBAI CO., LTD, EPASTAR 050W and 100W.

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

In the copper-carrying polymer particles, a coating film composed of a silane compound may be formed on at least a part of the surface of the polymer particles as the carrier. The silane compound is obtained by, for example, condensing a silicate compound described later.

The 2 nd metal-containing substance may be a solid substance or a liquid substance, but from the viewpoint of further improving the effect of the present invention, the 2 nd metal-containing substance is preferably a solid substance, and particles (particles present in the composition as particles) are preferable as the solid substance.

Among these, the 2 nd metal-containing substance is preferably the inorganic substance (2) and the 2 nd metal-supporting organic vehicle. More preferably a 2 nd metal-supported inorganic carrier or a 2 nd metal-supported organic carrier, and still more preferably a 2 nd metal-supported inorganic carrier.

When the 2 nd metal-containing material is a particle, the average particle diameter of the 2 nd 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. The average particle diameter of the metal-containing compound 2 is preferably 1.2 μm or less, more preferably 1.0 μm or less, further preferably 0.9 μm or less, further preferably 0.7 μm or less, particularly preferably 0.6 μm, most preferably 0.5 μm or less, further more preferably 0.3 μm or less, further most preferably 0.2 μm or less, and particularly preferably 0.15 μm or less. The lower limit is preferably 0.01 μm or more, more preferably 0.10 μm or more.

The method for measuring and adjusting the average particle size of the particles of the 2 nd metal-containing material can be the same as the method for measuring and adjusting the average particle size of the particles of the inorganic substance (1) described above.

When the 2 nd metal-containing substance is a particle, the aspect ratio is not particularly limited, but is preferably 1 to 40, more preferably 2 to 20.

The above aspect ratio can be calculated by the following method. First, of the 2 parallel straight lines circumscribing the 2 nd metal content, the 2 parallel straight lines having the largest distance between the straight lines are selected by an electron microscope, and the distance between the 2 parallel straight lines is defined as the major axis of the 2 nd metal content. Next, of the parallel 2 straight lines that are orthogonal to the major axis and that circumscribe the 2 nd metal content, the parallel 2 straight lines that minimize the distance between the straight lines are selected, and the distance between the parallel 2 straight lines is taken as the minor axis of the 2 nd metal content. The ratio of the long axis to the obtained short axis (long axis/short axis) is taken as a specific aspect ratio. The aspect ratio can be obtained by performing this operation on any 100 or more metal-containing materials of the 2 nd metal and arithmetically averaging the obtained specific aspect ratios.

As an example of a preferable embodiment of the composition, it is preferable that the 2 nd metal-containing substance contains an inorganic substance (2), both the inorganic substance (1) and the inorganic substance (2) are particles, both the inorganic substance (1) and the inorganic substance (2) have an average particle size of 1.5 μm or less, more preferably both the inorganic substance (1) and the inorganic substance (2) have an average particle size of 1.2 μm or less, still more preferably both the inorganic substance (1) and the inorganic substance (2) have an average particle size of 1.2 μm or less and the other has an average particle size of 0.9 μm or less, particularly preferably both the inorganic substance (1) and the inorganic substance (2) have an average particle size of 1.2 μm or less and the other has an average particle size of 0.6 μm or less, even more particularly preferably both the inorganic substance (1) and the inorganic substance (2) have an average particle size of 0.5 μm or less, the average particle size of either the inorganic substance (1) or the inorganic substance (2) is most preferably 0.5 μm or less and the average particle size of the other is 0.3 μm or less, and the average particle sizes of both the inorganic substance (1) and the inorganic substance (2) are most preferably 0.3 μm or less.

Another example of a preferable embodiment of the composition includes an embodiment in which the inorganic substance (1) contains a silver-containing substance and the 2 nd metal-containing substance contains a copper-containing substance. In the above composition, the mass ratio of the content of copper in the copper-containing substance to the content of silver in the silver-containing substance (the content of copper in the copper-containing substance/the content of silver in the silver-containing substance) is, for example, preferably 800 or less, more preferably 350 or less, further preferably 300 or less, preferably 0.1 or more, more preferably 5.0 or more, from the viewpoint of more excellent deodorant property and antibacterial property.

When the composition contains a silver-containing substance as the inorganic substance (1) and a copper-containing substance as the 2 nd metal-containing substance, from the viewpoint of deodorizing properties and antibacterial properties, it is preferable that both the silver-containing substance and the copper-containing substance are particles, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 1.5 μm or less, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 1.2 μm or less, that is, more preferably, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 1.2 μm or less, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 0.9 μm or less, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 0.6 μm or less, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 0.9 μm or less, that both the silver-containing substance and the copper-containing substance have an average particle diameter of 0.5 μm or The average particle diameter is 0.3 μm or less, and more preferably, the average particle diameters of the silver-containing substance and the copper-containing substance are both 0.3 μm or less.

In the above embodiment, the silver-containing substance as the inorganic substance (1) is preferably a silver-carrying inorganic carrier having a 1 st inorganic carrier and silver carried on the 1 st inorganic carrier, and more preferably a silver-carrying glass. The copper-containing substance as the 2 nd metal-containing substance is preferably 1 or more selected from the group consisting of a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier and a copper-carrying organic carrier having an organic carrier and copper carried on the organic carrier, and more preferably a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier.

Further, another example of a preferable embodiment of the composition includes a configuration in which the inorganic material (1) includes a silver-carrying inorganic carrier, the 2 nd metal-containing material includes a copper-containing substance (preferably 1 or more selected from the group consisting of a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier and a copper-carrying organic carrier having an organic carrier and copper carried on the organic carrier, and more preferably a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier), and zirconium phosphate.

Further, as an example of a preferable embodiment of the composition, there is a preferred embodiment in which the inorganic material (1) is a silver-carrying inorganic carrier and the 2 nd metal-containing substance is zirconium phosphate or phosphate glass.

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, preferably 10 μm or less, more preferably 5.0 μm or less. The average particle diameter of the metal-containing material of the 2 nd part is preferably 4.0 μm or less, more preferably 2.0 μm or less, further preferably 1.5 μm or less, particularly preferably 1.0 μm or less, most preferably 0.5 μm or less, preferably 0.01 μm or more, more preferably 0.1 μm or more. Of these, the average particle diameters of the inorganic substance (1) and the metal-containing substance (2) are preferably 0.9 μm or less (preferably 0.6 μm or less, more preferably 0.5 μm or less).

Further, as an example of a preferable embodiment of the composition, there is an embodiment in which the inorganic substance (1) is zirconium phosphate or phosphate glass, and the 2 nd metal-containing substance is a copper-containing substance (preferably 1 or more selected from the group consisting of a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier and a copper-carrying organic carrier having an organic carrier and copper carried on the organic carrier, and more preferably a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier).

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, most preferably 0.5 μm or less, preferably 0.01 μm or more, and more preferably 0.1 μm or more. The average particle diameter of the metal-containing material of the 2 nd part is preferably 0.01 μm or more, more preferably 0.2 μm or more, further preferably 0.3 μm or more, particularly preferably 0.5 μm or more, preferably 10 μm or less, more preferably 5.0 μm or less. Of these, the average particle diameters of the inorganic substance (1) and the metal-containing substance (2) are preferably 0.9 μm or less (preferably 0.6 μm or less, more preferably 0.5 μm or less).

< hydrophilic component >

The composition preferably contains a hydrophilic component selected from the group consisting of a hydrophilic binder precursor and a hydrophilic binder.

The content of the hydrophilic component in the composition is not particularly limited, but is preferably 20 to 99.8% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 99% by mass, based on the total solid content of the composition.

The hydrophilic component may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more hydrophilic components are used simultaneously, 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 2 nd metal-containing substance can be more firmly fixed to the substrate by the hydrophilic adhesive.

As a result, for example, even when the film is applied to an application such as a film in contact with a liquid, the inorganic substance (1) and the 2 nd metal-containing substance can be inhibited from flowing out of the film through the liquid. Specifically, even when the film is formed on a substrate such as a diaper, the inorganic material (1) and the metal-containing material (2) can be prevented from flowing out to the film through urine, and therefore, the antibacterial property and the deodorizing property can be continuously exhibited. Further, it is possible to suppress adverse effects on the skin caused by the outflow of the inorganic substance (1) and the metal-containing substance (2) to the outside of the film.

Further, the hydrophilic binder has high affinity with odorous substances such as ammonia and trimethylamine because of its hydrophilicity. Therefore, the hydrophilic adhesive also has a function of holding and diffusing the odorant on the surface of the film to increase the contact opportunity between the odorant and the inorganic material (1) and the metal-containing material (2). Further, according to the composition containing a hydrophilic component, it is easy to maintain excellent deodorizing properties for a longer period of time.

The hydrophilic binder precursor is a material capable of forming a hydrophilic binder by a curing reaction such as condensation and polymerization.

The hydrophilic binder is a material capable of forming a hydrophilic film capable of supporting the inorganic substance (1) and the 2 nd metal-containing substance. When a film composed of the hydrophilic adhesive is formed on a glass substrate, the hydrophilic adhesive has a water contact angle of preferably 60 ° or less, more preferably 50 ° or less, for example. The lower limit of the water contact angle is not particularly limited, but is preferably 5 ° or more.

In addition, the water contact angle was measured according to JIS R3257: 1999, the liquid drop method. Kyowa interface Science Co., Ltd., FAMMS DM-701 was used for the measurement.

The hydrophilic component is not particularly limited, and preferably at least 1 selected from the group consisting of 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, also referred to as a "hydrophilic polymer") from the viewpoint of more excellent fastness.

The monomer having a hydrophilic group means a compound having a hydrophilic group and a polymerizable group. When the composition contains a polymerization initiator described later, the hydrophilic monomer is polymerized to form a hydrophilic polymer.

The silicate compound, the hydrophilic monomer and the hydrophilic polymer will be described below.

(silicate compound)

In the present specification, the silicate-based compound means a compound selected from the group consisting of a compound having a hydrolyzable group bonded to a silicon atom, a hydrolysate thereof, and a hydrolysis-condensation product thereof, and examples thereof include at least 1 selected from the group consisting of a compound represented by the following formula (1), a hydrolysate thereof, and a hydrolysis-condensation product thereof.

Formula (1) Si- (OR)₄

In the formula (1), R represents alkyl groups having 1 to 4 carbon atoms, and may be the same or different.

Examples of the compound represented by the formula (1) include tetramethylsilicate, tetraethylsilicate, tetra-n-propylsilicate, tetraisopropylsilicate, tetra-n-butylsilicate, tetraisobutylsilicate, tetra-tert-butylsilicate, methylethylsilicate, methylpropylsilicate, methylbutylsilicate, ethylpropylsilicate, and propylbutylsilicate.

The hydrolysate of the compound represented by formula (1) refers to a compound obtained by hydrolyzing the OR group in the compound represented by formula (1). The hydrolysate may be a hydrolysate in which all OR groups are hydrolyzed (complete hydrolysate) OR a hydrolysate in which a part of OR groups are hydrolyzed (partial hydrolysate). That is, the hydrolysate may be a complete hydrolysate or a partial hydrolysate, or a mixture thereof.

The hydrolysis-condensation product of the compound represented by the formula (1) is a compound obtained by condensing a hydrolysate obtained by hydrolyzing an OR group in the compound represented by the formula (1). The hydrolysis-condensation product may be a hydrolysis-condensation product (complete hydrolysis-condensation product) in which all OR groups are hydrolyzed and all hydrolyzates are condensed, OR a hydrolysis-condensation product (partial hydrolysis-condensation product) in which a part of OR groups are hydrolyzed and a part of hydrolyzates are condensed. That is, the hydrolytic condensate may be a complete hydrolytic condensate or a partial hydrolytic condensate, or a mixture thereof.

The condensation degree of the hydrolysis-condensation product is preferably 1 to 100, more preferably 1 to 20, and still more preferably 3 to 15.

The compound represented by formula (1) is in a state in which at least a part thereof is hydrolyzed by mixing with a water component. The hydrolysate of the compound represented by formula (1) can be obtained by reacting the compound represented by formula (1) with a water component to convert an OR group bonded to silicon into a hydroxyl group. In the hydrolysis, it is not necessary to react all OR groups, but it is preferable that as many OR groups as possible are hydrolyzed in order to exhibit hydrophilicity after coating. The minimum amount of water required for hydrolysis is equal to the molar amount of the OR group of the compound represented by formula (1), but it is preferable that an excessive amount of water is present in order to smoothly progress the reaction.

The hydrolysis reaction of the silicate compound may be carried out at room temperature, but may be carried out at elevated temperature to promote the reaction. Further, a long reaction time is preferable because the reaction is accelerated. In the presence of a catalyst, a hydrolysate can be obtained in about half a day.

In addition, the hydrolysis reaction is generally a reversible reaction, and when water is removed from the system, the hydrolysate of the silicate compound begins to condense between hydroxyl groups. Therefore, when an excess amount of water is reacted with the silicate compound to obtain an aqueous solution of the hydrolysate, it is preferable to use the aqueous solution as it is without forcibly separating the hydrolysate.

Preferred examples of the silicate compound include compounds represented by the formula (X).

[ chemical formula 1]

Wherein, in the formula (X), R¹～R⁴Each independently represents an alkyl group having 1 to 4 carbon atoms. And n represents an integer of 2 to 100.

n is preferably 3 to 15, more preferably 5 to 10.

Examples of commercially available products of the silicate-based compound include COLCOAT CO., LTD. "Ethyl silicate 48", and Mitsubishi Chemical Corporation "MKC silicate MS 51".

The silicate compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(monomer having hydrophilicity (hydrophilic monomer))

The hydrophilic group is not particularly limited, and examples thereof include a polyoxyalkylene group (e.g., a polyoxyethylene group, a polyoxypropylene group, and a polyoxyalkylene group in which an oxyethylene group and a polyoxypropylene group are bonded in a block or random manner), an amino group, a carboxyl group, an alkali metal salt of a carboxyl group, a hydroxyl group, an alkoxy group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonic acid group, and an alkali metal salt of a sulfonic acid group. The number of hydrophilic groups in the hydrophilic monomer is not particularly limited, but is preferably 2 or more, more preferably 2 to 6, and further preferably 2 to 3, from the viewpoint of further developing hydrophilicity of the obtained film.

The polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group, a cation polymerizable group, and an anion polymerizable group. Examples of the radical polymerizable group include a (meth) acryloyl group, an acrylamide group, a vinyl group, a styryl group, and an allyl group. Examples of the cationically polymerizable group include a vinyl ether group, an ethylene oxide group, and an oxetane group. Among them, the polymerizable group is preferably a (meth) acryloyl group.

The number of the polymerizable groups in the hydrophilic monomer is not particularly limited, but is preferably 2 or more, more preferably 2 to 6, and further preferably 2 to 3, from the viewpoint of further improving the mechanical strength of the obtained film.

The structure of the main chain of the hydrophilic polymer formed by polymerization of the hydrophilic monomer is not particularly limited, and examples thereof include polyurethane, poly (meth) acrylate, polystyrene, polyester, polyamide, polyimide, polyurea, and the like.

The hydrophilic monomer can be used alone in 1 kind, also can be used simultaneously in more than 2 kinds.

(Polymer having hydrophilicity (hydrophilic Polymer))

The hydrophilic polymer is not particularly limited, and a known hydrophilic polymer can be used. In addition, the hydrophilic group is as defined above.

Examples of the hydrophilic polymer include polymers obtained by polymerizing the above-mentioned hydrophilic monomers. In addition to these, for example, a cellulose-based compound can be cited. The cellulose-based compound refers to a compound having cellulose as a matrix, and examples thereof include, in addition to carboxymethyl cellulose, nanofibers produced from 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, more preferably 10,000 to 500,000, from the viewpoint of better workability such as solubility. In the present specification, the weight average molecular weight is defined as a polystyrene equivalent value in Gel Permeation Chromatography (GPC) measurement.

The hydrophilic polymer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

< solvent >

The composition contains a solvent.

The content of the solvent in the composition is not particularly limited, and the solid content of the composition is preferably adjusted to 0.001 to 80% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5.0% by mass, from the viewpoint of more excellent coatability of the composition.

The solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more solvents are used simultaneously, the total content is preferably within the above range.

The solvent is not particularly limited, and water and/or an organic solvent may be used. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenethyl alcohol, octanol, lauryl alcohol, and myristyl alcohol; glycol ether solvents such as 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 monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether and the like; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, hexyl acetate, ethyl propionate, and butyl propionate; 10% bendinalinium alcohol solution, geraniol, sucrose octacetylate, strychnine, linalool, linalyl acetate, acetic acid and other hydrophilic solvents. From the viewpoint of easily suppressing elution of the metal contained in the inorganic substance (1) and the 2 nd metal-containing substance into the solvent, the solvent is preferably an alcohol, and more preferably ethanol or isopropanol.

In the composition, the content of the alcohol is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total mass of the composition, from the viewpoint of suppressing precipitation of the particulate matter and from the viewpoint of further improving the deodorizing property of the formed film. The upper limit is not particularly limited, and is, for example, preferably 99% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 45% by mass or less.

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, even more preferably 5 to 90% by mass, and particularly preferably 5 to 80% by mass, based on the total mass of the solvent.

< other ingredients >

The composition may contain other components within a range in which the effects of the present invention are exhibited. Examples of the other components include known additives such as a deodorant, an antibacterial agent, an ultraviolet absorber, an antiseptic agent, a pH adjuster, a defoaming agent, a polymerization initiator, a catalyst, a photocatalytic material, a surfactant, a filler, an antioxidant, an antistatic agent, a flame retardant, an adhesion-imparting agent, a leveling agent, a matting agent, a light stabilizer, a dye, a pigment, a dispersant, a fragrance, a film-forming agent, and a dispersion stabilizer.

Among them, 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 a known polymerization initiator can be used.

Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators.

Examples of the polymerization initiator include aromatic ketones such as benzophenone and phenylphosphine oxide, α -hydroxyalkylbenzophenone compounds (IRGACURE 184, 127, 2959, DAROCUR1173, etc. manufactured by BASF corporation), phenylphosphine oxide compounds (monoacylphosphine oxide IRGACURE TPO, IRGACURE819, manufactured by BASF corporation), and the like.

Among them, a photopolymerization initiator is preferable from the viewpoint of reaction efficiency.

The content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 6 parts by mass, based on 100 parts by mass of the hydrophilic monomer.

Further, 1 kind of polymerization initiator may be used alone, or 2 or more kinds may be used simultaneously. When 2 or more polymerization initiators are used simultaneously, the total content is preferably within the above range.

(dispersing agent)

When at least 1 of the inorganic substance (1) and the 2 nd metal-containing substance is in the form of particles, the composition preferably contains a dispersant.

The dispersant is not particularly limited, and a known dispersant can be used.

The dispersant is preferably a nonionic or anionic dispersant. From the viewpoint of affinity for the inorganic substance (1) and the 2 nd metal-containing substance, a dispersant (anionic dispersant) having an anionic polar group such as a carboxyl group, a phosphoric group, and a hydroxyl group is more preferable.

As the anionic dispersant, commercially available products can be used. Specific examples thereof include DISPERBYK (registered trademark) -110, DISPERBYK-111, DISPERBYK-116, DISPERBYK-140, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, and DISPERBYK-182, which are trade names of BYK-Chemie GmbH.

The content of the dispersant in the composition is not particularly limited, and is, for example, 70% by mass or less, preferably 50% by mass or less, based on the total solid content of the composition. The lower limit is not particularly limited, but is, for example, 0.01 mass% or more, and from the viewpoint of more excellent deodorization of the formed film, 1.0 mass% or more is preferable, and 15 mass% or more is more preferable.

The dispersant may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more dispersants are used simultaneously, the total content is preferably within the above range.

(catalyst)

When the composition contains a silicate compound, the composition may contain a catalyst (hereinafter, also referred to as a "reaction catalyst") for promoting condensation of the silicate compound.

The catalyst is not particularly limited, and examples thereof include an alkali catalyst and an organic metal catalyst.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and the like.

Examples of the organic metal catalyst include aluminum chelate compounds such as aluminum mono (acetylacetonate) bis (ethylacetoacetate), aluminum tris (acetylacetonate) and aluminum diisopropylacetoacetate, zirconium chelate compounds such as zirconium tetrakis (acetylacetonate) and bis (butoxy) bis (acetylacetonate), titanium chelate compounds such as titanium tetrakis (acetylacetonate) and bis (butoxy) bis (acetylacetonate), and organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate and dibutyltin dioctoate.

Among them, from the viewpoint that a composition having more excellent effects of the present invention can be obtained, an organometallic catalyst is preferable as the catalyst, and among them, an aluminum chelate compound or a zirconium chelate compound is more preferable, and an aluminum chelate compound is further preferable.

The content of the catalyst is preferably 0.1 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, based on 100 parts by mass of the total solid content of the composition.

Further, 1 kind of catalyst may be used alone, or 2 or more kinds may be used simultaneously. When 2 or more catalysts are used simultaneously, the total content is preferably within the above range.

(surfactant)

The composition may contain a surfactant. The surfactant has an 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, and is preferably 0.01 part by mass or more based on 100 parts by mass of the total solid content of the composition. The upper limit of the content of the surfactant is not particularly limited, but is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 4 parts by mass or less, per 100 parts by mass of the total solid content of the composition.

Further, 1 kind of surfactant may be used alone, or 2 or more kinds may be used simultaneously. When 2 or more are used simultaneously, the total content thereof is preferably within the above range.

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

Examples of the ionic surfactant include anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, and alkyl phosphates; cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts; amphoteric surfactants such as alkylcarboxy betaines.

(spice)

The composition may contain a perfume.

The perfume may include perfumes H-1, H-2, H-3, H-4, H-6, H-9, H-10, H-11, H-12, H-13, H-14, T-100, T-101, T-102, T-103, T-104, T-105, T-106, T-107, EDA-171, Soda Aromatic Co., Ltd. perfume S-201, RIKEN PERFURY HOLDING CO., Ltd. perfume DA-40, etc. manufactured by T.HASEGAWA CO., Ltd.

The content of the perfume is preferably 0.01 to 5% by mass based on 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 contain the silicate compound, the hydrophilic monomer, and the hydrophilic polymer.

Examples of the film-forming agent include thermoplastic resins. For example, when a film described later is formed, the film-forming agent functions as a binder.

The thermoplastic resin will be described below.

The thermoplastic resin is preferably a resin having a minimum film-forming temperature of 0 to 35 ℃, and a known thermoplastic resin can be used. Examples of the resin include a polyurethane resin, a polyester resin, (meth) acrylic resin, a polystyrene resin, a fluororesin, a polyimide resin, a fluorinated polyimide resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a cellulose acylate resin, a polyurethane resin, a polyether ether ketone resin, a polycarbonate resin, an alicyclic polyolefin resin, a polyarylate resin, a polyether sulfone resin, a polysulfone resin, a resin composed of a cycloolefin copolymer, a fluorene ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, and a fluorene ring-modified polyester resin. Among them, a (meth) acrylic resin or a urethane resin is preferable.

The thermoplastic resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the thermoplastic resin may be appropriately adjusted depending on the kind of the thermoplastic resin, and for example, is preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total solid content of the composition.

(antibacterial and deodorant)

The composition may contain, for example, an organic antibacterial agent such as a quaternary ammonium salt, a phenol ether derivative, an imidazole derivative, a sulfone derivative, an N-haloalkylthio compound, an anilide derivative, a pyrrole derivative, a pyridine compound, a triazine compound, a benzisothiazoline compound or an isothiazoline compound.

Further, as the deodorant, the composition may contain 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; butyl hydroxy anisole; hinokitiol; phenol; phenolic hydroxyl group-containing compounds such as tannic acid, persimmon tannin, and tea tannin.

Examples of the inorganic acid include phosphoric acid, sulfurous acid, sulfuric acid, and alkali metal salts thereof.

Examples of the organic acid include malic acid, citric acid, lactic acid, tartaric acid, salicylic acid, gluconic acid, adipic acid, phytic acid, fumaric acid, succinic acid, ascorbic acid, sorbic acid, glyoxylic acid, meldrum's acid, glutamic acid, ferulic acid, picric acid, aspartic acid, and alkali metal salts thereof. Among the organic acids, organic acids having a higher molecular weight are less likely to volatilize, and therefore the pH of the film surface formed using the composition is more likely to be maintained at 6.5 or less.

As the deodorant, malic acid or citric acid is preferable, and malic acid is more preferable, from the viewpoint that the volatilization is more difficult and the deodorant property is more excellent.

Further, when a compound having an antioxidant function (for example, a salt of a fluidizer, ferulic acid, dibutylhydroxytoluene, butylhydroxyanisole, ascorbic acid, or the like) is used as a deodorant, the change in the quality of the inorganic substance (1) and the metal-containing component (2) can be more easily suppressed, and the antibacterial property and the deodorizing property of the film can be more excellent.

Further, as the deodorant, it is also preferable to use a deodorant having an antioxidant function and a deodorant other than the deodorant having an antioxidant function together. When a deodorant having an antioxidant function and a deodorant other than the deodorant having an antioxidant function are used simultaneously, the antibacterial property and the deodorizing property of the film last for a longer time.

< pH of composition >

The pH of the composition is not particularly limited, and is preferably adjusted within an appropriate range in consideration of chapping of hands of a user in an actual use environment, and the like.

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, as the inorganic material (1) and the 2 nd metal-containing material, for example, a component dissolved in an acid or an alkali or a component easily deteriorated, the composition has more excellent effects of the present invention when the pH of the composition is within the above range.

Further, as a method for adjusting the pH of the composition, a method of adding an acid or an alkali to the composition is exemplified.

The pH can be measured at 25 ℃ with a commercially available pH meter (e.g., a pH meter HM-30R manufactured by DKK-TOA CORPORATION).

< specific gravity of composition >

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

< viscosity of composition >

The viscosity of the composition is not particularly limited, and may be adjusted according to the use.

For example, when the composition is applied to coating, spraying or the like, the viscosity at 25 ℃ of the composition is preferably 300cP (centipoise: 1cP ═ 1 mPas) or less, more preferably 200cP or less, and still more preferably 0.1 to 150 cP.

Further, when the antibacterial and deodorant effects are maintained for a long period of time, the viscosity of the composition at 25 ℃ is preferably 250cP or more, more preferably 300cP or more, and still more preferably 400cP or more. The upper limit is, for example, 500cP or less.

The viscosity can be measured by Toki Sangyo Co., Ltd, VISCOMETER TUB-10 manufactured by Ltd, or SEKONIC VISCOMETER manufactured by SEKONICCORPORATION.

< ZETA potential of composition >

The ZETA potential of the composition is not particularly limited, and is preferably adjusted to an appropriate range in consideration of a more excellent resistance to sedimentation due to a proper dispersion of the particulate matter in the composition. The ZETA potential of the composition is preferably 80mV to-80 mV, more preferably 70mV to-70 mV, and still more preferably 60mV to-60 mV.

The ZETA potential can be measured by a known method, and a predetermined amount of the dispersion can be introduced into a dedicated measuring cell made of glass and measured by Otsuka Electronics co., ltd.

< method for producing composition >

The composition may further contain other additives as necessary within a range in which the effects of the present invention are exhibited.

The composition can be prepared by appropriately mixing the essential components and optional components. The mixing order of the above components is not particularly limited.

< use of the composition >

The above composition can be used to form a film.

The method for forming the film is not particularly limited, and a method (coating method) in which the composition is applied to a desired substrate or article to form a coating film, and the coating film is dried or cured to form a film is preferable.

The method of applying the above composition to a desired substrate or article is not particularly limited. Examples thereof include spray coating, roll coating, gravure coating, screen coating, spin coating, flow coating, ink jet, electrostatic coating, and wipe coating. Among them, from the viewpoint of enabling a film to be formed on the surface of an existing article as needed for treatment (on-demand treatment), spraying or wiping is preferable, and wiping is more preferable.

The method of forming the film by wiping is not particularly limited, and a known method can be used. For example, the following methods can be mentioned. First, a base fabric such as a nonwoven fabric is impregnated with the composition, and then the surface of a substrate or an article is wiped with the base fabric. Thereby, a coating film based on the above composition is formed on the surface of the substrate or article. Thereafter, the formed coating film is dried or cured to obtain a film.

Further, according to the composition, as described later, a modified base material having excellent deodorant properties and antibacterial properties can be formed. When a modified substrate is obtained using the above composition, 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 comprises an inorganic substance (1) and a metal-containing substance (2).

< inorganic substance (1) >

The inorganic material (1) is the same as the inorganic material (1) contained in the composition, and the preferable embodiment is also the same.

< 2 nd Metal content >

The content of the 2 nd metal is the same as that of the 2 nd metal content contained in the composition, and the preferable embodiment is also the same.

< hydrophilic adhesive >

The membrane preferably contains a hydrophilic binder. The hydrophilic binder is not particularly limited, and examples thereof include a hydrolysate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a hydrolysis-condensation product thereof; the polymer having a hydrophilic group and the like is preferably at least 1 selected from the group consisting of a hydrolysate of a compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof.

Preferred embodiments of the compound in which a hydrolyzable group is bonded to a silicon atom and preferred embodiments of the polymer having a hydrophilic group are as described above.

< other ingredients >

The film may further comprise ingredients other than the above ingredients.

< method for producing film >

The film of the present invention can be obtained, for example, by drying or curing the above-mentioned composition. The above composition is as described above.

Further, when the composition contains a hydrophilic binder precursor as a hydrophilic component, a coating film (composition layer) of the film curable composition is obtained. In other words, the above film can be obtained by treating the composition layer with a hydrophilic adhesive precursor as a hydrophilic adhesive by the curing treatment of the composition layer.

In contrast, when the hydrophilic component in the composition is a hydrophilic adhesive, the composition does not need to be subjected to a curing treatment.

< film thickness of film >

The film thickness is not particularly limited, but is preferably 0.001 to 50 μm, more preferably 0.01 to 10 μm.

The film thickness is: a sample piece of the film was embedded in a resin, a cross section was cut with a microtome, the cut cross section was observed and measured with a scanning electron microscope, the thickness of any 10-point position of the film was measured, and the value was arithmetically averaged.

< pH of the Membrane >

The membrane surface pH is typically preferably 7.0 or less, and from the viewpoint of more excellent deodorizing properties particularly against odorous substances derived from urine, feces, and the like such as ammonia and trimethylamine, is preferably 6.5 or less, more preferably 5.0 or less, and still more preferably 4.5 or less. 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, the membrane surface pH of the membrane is as follows: the value was determined by dropping 0.02mL of a liquid droplet (pure water) onto the membrane surface and measuring the pH of the liquid droplet with a pH meter LAQUA F-72 manufactured by HORIBA, Ltd.

As described later, the film can be suitably used for diapers and the like. In this case, when the pH of the membrane surface is set to the above numerical range (preferably, pH of 6.5 or less), the metals in the inorganic substance (1) and the metal-containing substance 2 contained in the membrane are less likely to be deteriorated, and the antibacterial property and the deodorant property are more excellent.

Examples of the membrane having the membrane surface pH within the above numerical range include membranes containing an inorganic substance (1), a 2 nd metal-containing substance, and an organic acid. Since the organic acid has low volatility, it adheres to the hydrophilic adhesive in a dry state. When a liquid containing an odorant such as urine adheres to the membrane surface, the organic acid on the membrane surface is dissolved by the liquid containing the odorant, and the membrane surface pH is likely to be in the above range. In this way, the pH of the membrane surface does not become too low in the state before the odorous substance-containing liquid is attached, and the metals in the inorganic substance (1) and the metal-containing substance (2) contained in the membrane are not easily deteriorated.

Further, another example of the film having the film surface pH within the above numerical range includes a film containing a microcapsule having a compound or the like (which may be the organic acid) having a pH adjusting function and dissolved in a liquid containing an odor substance, and the like contained in the film. When the liquid containing the odorant is adhered to the film surface of the film containing the microcapsules, the film of the microcapsules is dissolved and the compound having the pH adjusting function is exposed to the film surface, whereby the pH of the film surface of the film is likely to fall within the above range. In this case, the pH of the membrane surface does not become too low in the state before the deposition of the odorous substance-containing liquid, and the metals in the inorganic substance (1) and the metal-containing substance (2) contained in the membrane are not easily deteriorated.

[ substrate with film ]

The film-equipped substrate according to the embodiment of the present invention includes a substrate and the film. The film-attached substrate may be a laminate including a substrate and a film, and the film may be provided on one surface of the substrate or on both surfaces of the substrate.

< substrate >

The substrate functions as a support film, and the kind thereof is not particularly limited.

The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, a fiber shape, and a particle shape.

The material constituting the substrate is not particularly limited, and examples thereof include metal, glass, ceramic, and plastic (resin). Among them, plastic is preferable from the viewpoint of workability. In other words, as the substrate, a resin substrate is preferable.

[ method for producing base with film ]

The method for producing a film of the present invention corresponds to a method for producing a film using the above composition, and comprises the following steps.

(1) When the composition contains a hydrophilic binder precursor as a hydrophilic component, the composition has the following steps a and b.

(2) When the composition contains a hydrophilic binder as the hydrophilic component, the composition has the following step a.

(step A) Process for applying the composition to the surface of a substrate to form a composition layer

(step B) Process for obtaining a film by curing the composition layer

Hereinafter, the steps a and B will be described.

(Process A)

The step a is a step of applying the composition to the surface of the substrate to form a composition layer. The method for applying the composition to the surface of the substrate is not particularly limited, and a known coating method can be used.

The method for applying the composition to the surface of the substrate includes the above-mentioned methods.

The thickness of the composition layer is not particularly limited, and is preferably 0.001 to 10 μm as a dry film thickness.

After the composition is applied, a heat treatment may be performed to remove the solvent. In this case, the conditions for the heat treatment are not particularly limited, and for example, the heating temperature is preferably 50 to 200 ℃ and the heating time is preferably 15 to 600 seconds.

The substrate that can be used in step a is the same as the substrate described above.

(Process B)

The step B is a step of curing the composition layer to obtain a film. That is, the step of using the hydrophilic adhesive precursor contained in the composition layer as a hydrophilic adhesive by a curing reaction such as condensation or polymerization.

The method for curing the composition layer is not particularly limited, and examples thereof include heat treatment and/or exposure treatment.

The exposure treatment is not particularly limited, and examples thereof include irradiation with an ultraviolet lamp at 100 to 600mJ/cm²The composition layer is cured by ultraviolet rays of the irradiation amount of (3).

In the case of ultraviolet irradiation, ultraviolet rays emitted from light rays such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a xenon arc lamp, and a metal halide lamp can be used.

The temperature of the heat treatment is not particularly limited, and is, for example, preferably 50 to 150 ℃ and more preferably 80 to 120 ℃.

[ modified substrate ]

The modified substrate of the present invention comprises a substrate, an inorganic material (1) disposed on or in the substrate, and a component containing a metal 2.

In addition, when the modified substrate of the present invention contains the inorganic substance (1) and the component containing the 2 nd metal on the substrate, the modified substrate of the present invention is also preferably configured to have a substrate, the inorganic substance (1) disposed on the substrate, the component containing the 2 nd metal, and a hydrophilic binder.

The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a film shape, a sheet shape, a tube shape, a fiber shape, and the like. The fibrous form as used herein refers to a fiber and a structure such as a two-dimensional structure or a three-dimensional structure formed by the fiber (for example, a fabric-like body such as a woven fabric or a nonwoven fabric).

The material constituting the substrate is not particularly limited, and examples thereof include natural resins and synthetic resins.

Hereinafter, embodiments of modifying the substrate will be described.

For example, when the substrate is a fiber, the modified substrate may be a fiber having a fiber, and the inorganic material (1) and the 2 nd metal-containing component attached to the surface of the fiber.

When the substrate is a fiber structure, examples of the modified substrate include a mode having a fiber structure and inorganic materials (1) and a 2 nd metal-containing component attached to the surface of the fiber structure, and a mode having a fiber structure and inorganic materials (1) and a 2 nd metal-containing component disposed inside the fiber structure. When the base material is a fiber or a fiber structure, the content of the inorganic material (1) and the 2 nd metal-containing component in the modified base material is preferably 0.0001 to 10% by mass based on the mass of the fiber or the fiber structure.

The method for forming the modified substrate in which the substrate is a fiber or a fiber structure is not particularly limited, and examples thereof include a method in which the composition is applied to a fiber or a fiber structure by a method such as impregnation or blowing, and then dried to form a modified substrate. When the composition contains a hydrophilic binder precursor, the composition may be subjected to heat treatment and/or exposure treatment.

Another example of a method for forming a modified substrate as a fibrous structure includes a method in which a fibrous material such as wood pulp and the above composition are mixed to prepare a slurry, and the slurry is used as a raw material to form a modified substrate having a fibrous structure, an inorganic material (1) disposed in the fibrous structure, and a component containing a metal of the 2 nd group by a wet papermaking method.

The modified substrate may be, for example, a resin-made molded body (e.g., a sheet-like molded body), and the inorganic material (1) and the 2 nd metal-containing component may be disposed inside the molded body. The resin is not particularly limited, and examples thereof include synthetic resins (water-absorbing polymers such as sodium polyacrylate). The modified substrate according to the above embodiment can be formed using the above composition. Specific examples of the production method include a method in which the composition is cast to form a cast film, and then dried, heated and/or cured. In the case where the modified substrate according to the above embodiment is formed using the above composition, the composition preferably further contains a polymer, a curable compound, and the like. The polymer and the curable compound are not particularly limited, and examples thereof include sodium polyacrylate and the like.

< inorganic substance (1) >

< 2 nd Metal content >

< combination of inorganic substance (1) and metal-containing substance (2) >)

The combination of the inorganic substance (1) and the 2 nd metal-containing substance is also the same as the preferable embodiment of the combination of the inorganic substance (1) and the 2 nd metal-containing substance in the composition described above.

< hydrophilic adhesive >

The modified substrate preferably contains a hydrophilic binder. The hydrophilic binder is not particularly limited, and examples thereof include a hydrolysate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a hydrolysis-condensation product thereof; the polymer having a hydrophilic group and the like is preferably at least 1 selected from the group consisting of a hydrolysate of a compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof.

Preferred embodiments of the compound in which a hydrolyzable group is bonded to a silicon atom and preferred embodiments of the polymer having a hydrophilic group are the same as the preferred embodiments described as the hydrophilic component that can be contained in the composition.

< other ingredients >

The modified substrate may further contain components other than the above components.

[ Wet wipes ]

The wet wiping cloth according to the embodiment of the invention comprises a base fabric and a composition impregnated into the base fabric. The above composition is as described above.

The base fabric is not particularly limited, and may be a base fabric made of natural fibers or a base fabric made of chemical fibers.

Examples of the natural fibers include wood pulp, cotton, hemp, flax, wool, camel hair, cashmere, mohair, and silk.

Examples of the material of the chemical fiber include rayon, kapok (Polynosic), acetic acid, triacetic acid, nylon, polyester, polyacrylonitrile, polyvinyl alcohol, vinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyurethane, sodium Polyalkylene paraben (Polyalkylene paraoxybenzoate), polyvinyl chloride (polychlalal), and the like.

Among these, hydrophilic base fabrics are preferable from the viewpoint of ease of impregnation with the composition. The hydrophilic base is a base containing fibers having a hydrophilic group such as a hydroxyl group, an amino group, a carboxyl group, an amide group, and a sulfonyl group. Specific examples of the hydrophilic base fabric include plant fibers, cotton, wood pulp, animal fibers, rayon, nylon, polyester, polyacrylonitrile, and polyvinyl alcohol.

As the base fabric of the wet wipe cloth, a nonwoven fabric, a cloth, a towel, a gauze, a cotton wool, and the like can be used, and a nonwoven fabric is preferable.

Further, the weight (mass per unit area) of the base fabric is preferably 100g/m²The following. The impregnation amount of the composition into the base fabric is preferably 1 time or more of the mass of the base fabric.

[ spraying ]

A spray coater according to an embodiment of the present invention includes a spray container and a composition stored in the spray container. The above composition is as described above.

The spray coater of the present invention may be a spray coater that fills a predetermined container with the composition and the propellant. The propellant to be used is not particularly limited, and examples thereof include liquefied petroleum gas.

[ composition (reference example) ]

The present inventors also found that a film having excellent antibacterial properties and excellent deodorizing properties can be formed by a composition comprising a 1 st metal-loaded inorganic carrier, a 1 st metal-loaded organic carrier, and a solvent (hereinafter, also referred to as "composition (reference example)").

Among them, the 1 st metal is not particularly limited, and silver or copper is more preferable, and copper is particularly preferable.

< Supported No. 1 Metal inorganic support >

The inorganic support carrying the 1 st metal inorganic support is the same as the inorganic support carrying the 1 st metal inorganic support that can be contained in the composition of the embodiment described above, and the preferred embodiment is also the same.

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

The aspect ratio of the 1 st metal-loaded inorganic carrier is not particularly limited, but is preferably 1 to 40, and more preferably 2 to 20. In addition, the aspect ratio can be calculated by the above-described method.

The content of the 1 st metal-loaded inorganic carrier in the composition (reference example) is not particularly limited, but is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, and still more preferably 0.1 to 10% by mass, based on the total solid content of the composition.

< Supported 1 st Metal organic vehicle >

The organic vehicle carrying the 1 st metal organic vehicle is not particularly limited, and examples thereof include polymer particles.

Specific examples of the metal-organic vehicle 1 include polymer particles (copper-carrying polymer) carrying copper particles or copper oxide particles.

The copper-supporting polymer is the same as the copper-supporting polymer exemplified as the specific example of the 2 nd metal-supporting organic vehicle that can be contained in the composition of the embodiment described above.

The average particle diameter of the 1 st metal-organic carrier is not particularly limited, but is usually preferably 0.01 μm or more, more preferably 0.2 μm or more, and still more preferably 0.5 μm or more. The upper limit is preferably 3.0 μm or less, more preferably 1.0 μm or less. In addition, in view of the precipitation property of the 1 st metal-organic carrier or the transparency of the composition, the 1 st metal-organic carrier having a small average particle diameter is preferable because the dispersibility is excellent and, as a result, the transparency of the composition is high. In this case, the average particle diameter of the 1 st metal-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 adhesive agent described later, the 1 st metal-organic support can be easily fixed to a film formed from the composition (reference example) in a state where the 1 st metal-organic support is exposed from the hydrophilic adhesive agent, by setting the average particle diameter of the 1 st metal-organic support to the above numerical range. Therefore, the metal is more easily released from the carrier, and the antibacterial property and the deodorizing property of the film are further excellent.

The method for measuring the average particle diameter of the 1 st metal-organic carrier is the same as the method for measuring the average particle diameter of the inorganic substance (1) that can be contained in the composition of the embodiment described above.

The content of the 1 st metal-organic vehicle in the composition (reference example) is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.01 to 40% by mass, based on the total solid content of the composition.

< solvent >

The kind of the solvent is not particularly limited, and the same solvent as that described as the solvent that can be contained in the composition of the embodiment described above can be used.

< hydrophilic adhesive >

The composition (reference example) may contain a hydrophilic component.

The hydrophilic component is the same as the hydrophilic component described as the hydrophilic component that can be contained in the composition of the embodiment described above, and the preferred embodiment is also the same.

< other ingredients >

The composition (reference example) may contain other ingredients.

The other components are the same as those contained in the composition of the embodiment described above, and the preferred embodiment is also the same.

< Property of composition (reference example) >

The 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) are the same as those described as the physical properties (pH of the composition, specific gravity of the composition, viscosity of the composition, and ZETA potential of the composition) of the composition of the embodiment described above, and preferred embodiments are also the same.

< method for producing composition (reference example) and use thereof >

The method for producing the composition (reference example) and the use thereof are the same as those described as the method for producing the composition according to the embodiment and the use thereof, and the preferred embodiment is the same.

[ film (reference example) ]

Further, the present inventors found that a film comprising the 1 st metal-supported inorganic carrier and the 1 st metal-supported organic carrier (hereinafter, also referred to as "film (reference example)") has excellent antibacterial properties and excellent deodorizing properties.

< Supported No. 1 Metal inorganic support >

The 1 st metal-loaded inorganic carrier is the same as the 1 st metal-loaded inorganic carrier contained in the composition described above (reference example), and the preferred embodiment is also the same.

< Supported 1 st Metal organic vehicle >

The 1 st metal-organic carrier is the same as the 1 st metal-organic carrier contained in the composition described above (reference example), and the preferred embodiment is the same.

< hydrophilic adhesive >

The film (reference example) preferably contains a hydrophilic binder. The hydrophilic binder is not particularly limited, and examples thereof include a hydrolysate of a compound in which a hydrolyzable group is bonded to a silicon atom, and a hydrolysis-condensation product thereof; the polymer having a hydrophilic group and the like is preferably at least 1 selected from the group consisting of a hydrolysate of a compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof.

Preferred embodiments of the compound in which a hydrolyzable group is bonded to a silicon atom and preferred embodiments of the polymer having a hydrophilic group are the same as those of the composition of the embodiment described above.

< other ingredients >

The film (reference example) may further contain components other than the above components.

< method for producing Membrane (reference example) >

The film of the present invention can be obtained by, for example, drying or curing the above-mentioned composition (reference example). The above composition (reference example) is as described above.

In addition, when the composition (reference example) contains a hydrophilic binder precursor as a hydrophilic component, the film (reference example) can be obtained by curing a coating film (composition layer) of the composition (reference example). In other words, the above-described film (reference example) can be obtained by treating the composition layer with a hydrophilic adhesive precursor as a hydrophilic adhesive by the curing treatment of the composition layer.

In contrast, when the hydrophilic component in the composition (reference example) is a hydrophilic adhesive, it is not necessary to perform a 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, more preferably 0.01 to 10 μm.

< pH of the Membrane (reference example) >

The membrane (reference example) typically has a membrane surface pH of preferably 7.0 or less, and from the viewpoint of more excellent deodorizing properties particularly against odorous substances derived from urine, feces, and the like, such as ammonia and trimethylamine, preferably 6.5 or less, more preferably 5.0 or less, and still more preferably 4.5 or less. 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, the membrane surface pH of the membrane (reference example) is as follows: the value was determined by dropping 0.02mL of a liquid droplet (pure water) onto the membrane surface and measuring the pH of the liquid droplet with a pH meter LAQUA F-72 manufactured by HORIBA, Ltd.

As described later, the film (reference example) can be suitably used for a diaper and the like. In this case, when the pH of the film surface is set to the above numerical range (preferably, pH of 6.5 or less) when the odor substance-containing liquid such as urine is adhered to the film surface, the metals in the 1 st metal-loaded inorganic carrier and the 1 st metal-loaded organic carrier contained in the film (reference example) are less likely to be deteriorated, and the antibacterial property and the deodorant property are more excellent.

Examples of the membrane having a membrane surface pH in the above numerical range include membranes containing a 1 st metal inorganic carrier, a 1 st metal organic carrier, and an organic acid. Since the organic acid has low volatility, it adheres to the hydrophilic adhesive in a dry state. When a liquid containing an odorant such as urine adheres to the membrane surface, the organic acid on the membrane surface is dissolved by the liquid containing the odorant, and the membrane surface pH is likely to be in the above range. In this way, the pH of the membrane surface does not become too low in the state before the deposition of the odorous substance-containing liquid, and the metals in the 1 st metal-loaded inorganic carrier and the 1 st metal-loaded organic carrier contained in the membrane are not easily deteriorated.

Further, another example of the film having the membrane surface pH in the above numerical range is a method in which microcapsules having a coating film dissolved in a liquid containing an odorant, a compound having a pH adjusting function contained in the coating film, and the like (the organic acid may be used). When the liquid containing the odorant is adhered to the film surface of the film containing the microcapsules, the film of the microcapsules is dissolved and the compound having the pH adjusting function is exposed to the film surface, whereby the pH of the film surface of the film is likely to fall within the above range. In this case, the pH of the membrane surface does not become too low in the state before the deposition of the odorous substance-containing liquid, and the metals in the 1 st metal-loaded inorganic carrier and the 1 st metal-loaded organic carrier contained in the membrane are not easily deteriorated.

[ base Material with Membrane (reference example) ]

The film-equipped substrate (reference example) had a substrate and the film (reference example). The film-attached substrate (reference example) may be a laminate including a substrate and a film (reference example), and may have a film on one surface of the substrate (reference example) or may have a film on both surfaces of the substrate (reference example).

< substrate >

The substrate functions as a support film (reference example), and the kind thereof is not particularly limited.

The substrate is the same as that used for the film-coated substrate of the embodiment described above.

[ method for producing base with film (reference example) ]

The method for producing a film-coated substrate (reference example) corresponds to the method for producing a film (reference example) using the composition (reference example), and comprises the following steps.

(1) When the composition (reference example) contains a hydrophilic binder precursor as a hydrophilic component, the following steps are included.

(2) When the composition (reference example) contains a hydrophilic binder as the hydrophilic component, it has the following step a.

(step A) Process for applying the composition (reference example) to the surface of a substrate to form a composition layer

(step B) Process for obtaining a film (reference example) by curing the composition layer

The specific procedure of the method for producing a film-coated substrate (reference example) is the same as that of the method for producing a film-coated substrate according to the embodiment described above.

[ Wet wiping cloth (reference example) ]

The wet wiping cloth (reference example) has a base cloth and a composition (reference example) impregnated into the base cloth. The above composition (reference example) is as described above.

The specific structure of the wet wipe (reference example) is the same as that of the wet wipe according to the embodiment described above, except that the composition used is different.

[ spraying (reference example) ]

The spray coater (reference example) had a spray container and a composition (reference example) contained in the spray container. The above composition (reference example) is as described above.

Except for the difference in the composition used, the specific configuration of the coating machine (reference example) is the same as that of the coating machine according to the embodiment described above.

Examples

The present invention will be described in more detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the treatments, the procedures of the treatments, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. The scope of the invention should therefore not be interpreted restrictively by the examples shown below.

[ example 1: preparation of composition 1]

In a vessel, while stirring 367g of ethanol, 60g of pure water, 14g of a silicate compound ("MKC (registered trademark) silicate" MS51 "manufactured by Mitsubishi Chemical Corporation), 15g of aluminum chelate D (bis (ethyl acetoacetate) mono (acetylacetone) aluminum, 15g of ethanol diluted so as to have a solid content concentration of 1 mass%), 10g of a nonionic surfactant (NIHON EMULSION Co., manufactured by Ltd.," EMLEX 715 "manufactured by Ltd., pure water diluted so as to have a solid content concentration of 0.5 mass%), and an anionic surfactant (bis (2-ethylhexyl) sodium sulfosuccinate, 10g of pure water diluted so as to have a solid content concentration of 0.2 mass%), 18g of isopropyl alcohol, 3.6g of a dispersant (DISPERBYK (registered trademark) -180" manufactured by BYK-GmbH), and silver-loaded glass particles (Fuji Ltd., manufactured by Chemical), ethanol dilution: solid content concentration 60 mass%) 2.4g, and stirred for 20 minutes, thereby obtaining a dispersion a.

The silver-loaded glass particles in the dispersion a correspond to the inorganic material (1).

To the obtained dispersion a, 0.28g of copper-carrying glass (corresponding to TOAGOSEI co., ltd. "NS-20C" (inorganic substance (2); and inorganic carrier corresponding to "NS-20℃", ltd.)) was added as a 2 nd metal-containing substance and stirred, thereby obtaining a composition 1.

The obtained composition 1 of example 1 contained an inorganic substance (1), a 2 nd metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.

(average particle diameter of inorganic substance (1) and Metal-containing substance No. 2)

When the inorganic substance (1) and the 2 nd metal-containing substance are particles, the average particle diameter of the particles is measured by observation with 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 properties according to the tests shown below.

First, a nonwoven fabric was prepared, and the composition 1 was sprayed onto the nonwoven fabric so that the nonwoven fabric was per 100cm²1g of composition 1 was attached. Subsequently, the obtained nonwoven fabric with the composition 1 was dried at 25 ℃ for 2 days, thereby producing a film base material 1.

(evaluation of deodorizing ability)

10g of urine emitting ammonia odor was sprayed onto the film-attached substrate 1, and the substrate was left at room temperature. After standing, the odor was evaluated organoleptically after 1 hour and after 8 hours. The results are shown in Table 1.

Reference to evaluation

"A": almost no odor was smelled.

"B": smelling the odor slightly.

"C": smelling the odor slightly.

"D": smelling odor.

"E": smelling the odor strongly.

(evaluation of antibacterial Properties)

The antibacterial properties of the film-coated substrate 1 were evaluated.

For evaluation of antibacterial properties, according to JIS Z2801: 2012, the contact time with the bacterial suspension was changed to 24 hours by using coliform bacteria, and the test was performed. The antibacterial activity value after the test was measured and evaluated according to the following evaluation criteria. The results are shown in Table 1.

Reference to evaluation

"A": the antibacterial activity value is more than 2.5

"B": the antibacterial activity value is more than 1.0 and less than 2.5

"C": antibacterial activity value less than 1.0

(Membrane surface pH)

The antibacterial properties of the film-coated substrate 1 were evaluated. The evaluation method was as described above.

Comparative example 1: preparation of composition R1 ]

A composition R1 of comparative example 1 was prepared in the same manner as in example 1, except that the 2 nd metal-containing substance was not used and the average particle size of the inorganic substance (1) was adjusted to the size (μm) shown in table 1.

Using the obtained composition R1, various evaluations were carried out in the same manner as in composition 1. The results are shown in Table 1.

[ example 2: preparation of composition 2 ]

Composition 2 was prepared and evaluated in the same manner as in example 1, except that the average particle diameters of the inorganic substance (1) and the 2 nd metal-containing substance were adjusted to the sizes shown in table 1. The results are shown in Table 1.

[ example 3: preparation of composition 3 ]

Composition 3 was prepared and evaluated in the same manner as in example 2, except that the MKC silicate MS51 was not used. The results are shown in Table 1.

Comparative example 2: preparation of composition R2 ]

Composition R2 was prepared and evaluated in the same manner as in comparative example 1, except that the MKC silicate MS51 was not used. The results are shown in Table 1.

Comparative example 3: preparation of composition R3 ]

Except that no silver-carrying glass was used, a composition R3 was prepared and evaluated in the same manner as in example 3. The results are shown in Table 1.

Table 1 is shown below.

The "copper-carrying glass" in table 1 is toagososeico, ltd, manufactured as "NS-20C", in which the average particle diameter is controlled to the size described in the table. The inorganic carrier manufactured by TOAGOSEI CO., LTD. "NS-20C" is equivalent to aluminum silicate.

[ Table 1]

From the above results, it is understood that the compositions of examples 1 to 4 containing the inorganic substance (1), the 2 nd 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 2 nd metal-containing substance and the composition of comparative example 3 containing no inorganic substance (1) did not exhibit the effect of the present invention.

Further, it is found that the composition of example 2 containing the hydrophilic component maintains more excellent deodorizing property even after 8 hours has elapsed, as compared with the composition of example 3.

[ example 4: preparation of composition 4 ]

Composition 4 was prepared in the same manner as in example 1 except that the average particle diameter of the inorganic substance (1), and the average particle diameter and aspect ratio of the 2 nd metal-containing substance were adjusted to the values shown in table 2.

Using the thus-prepared composition 4, the evaluation < evaluation B > described later was carried out, and the results are shown in Table 2. Further, the < evaluation B > described later is set to a more strict evaluation condition than the < evaluation a > described above.

< evaluation of B >

(preparation of test sample)

The composition 4 obtained above was evaluated for its deodorizing properties according to the tests shown below.

First, a nonwoven fabric was prepared, and the composition 4 was sprayed onto the nonwoven fabric so that the nonwoven fabric was per 100cm²0.1g of composition 4 was attached. Subsequently, the obtained nonwoven fabric with the composition 4 was dried at 25 ℃ for 2 days, thereby producing a film-attached substrate 4.

(evaluation of deodorizing ability)

10g of urine emitting ammonia odor was sprayed onto the film-attached substrate 4, and the film-attached substrate was left at room temperature. After standing, the odor was evaluated organoleptically after 1 hour and after 8 hours. The results are shown in Table 1.

Reference to evaluation

"AA": the odor was smelled only very weakly.

"A": almost no odor was smelled.

"B": smelling the odor slightly.

"C": smelling the odor slightly.

"D": smelling odor.

"E": smelling the odor strongly.

(evaluation of antibacterial Properties)

The antibacterial properties of the film-coated substrate 4 were evaluated.

For evaluation of antibacterial properties, according to JIS Z2801: 2012, the test was carried out using coliform bacteria, and the contact time with the bacterial suspension was changed to 24 hours. The antibacterial activity value after the test was measured and evaluated according to the following evaluation criteria. The results are shown in Table 2.

Reference to evaluation

"A": the antibacterial activity value is more than 2.5

"B": the antibacterial activity value is more than 1.0 and less than 2.5

"C": antibacterial activity value less than 1.0

(Membrane surface pH)

The antibacterial properties of the film-coated substrate 4 were evaluated. The evaluation method was as described above.

[ example 5: preparation of composition 5 ]

Composition 5 was prepared and evaluated in the same manner as in example 4, except that the average particle diameter and the aspect ratio of the metal content 2 were adjusted to the values shown in table 2. The results are shown in Table 2.

[ example 6: preparation of composition 6 ]

Composition 6 was prepared and evaluated in the same manner as in example 4, except that the average particle diameter and the aspect ratio of the metal content 2 were adjusted to the values shown in table 2. The results are shown in Table 2.

[ example 7: preparation of composition 7 ]

Composition 7 was prepared and evaluated in the same manner as in example 4, except that the average particle diameter of the inorganic substance (1), and the average particle diameter and aspect ratio of the 2 nd metal-containing substance were adjusted to the values shown in table 2. The results are shown in Table 2.

The results of the above evaluation B using the above compositions 1 and 2 are also shown in table 2.

The "copper-carrying glass" in table 2 is manufactured by toagososeico, ltd, NS-20C, which controls the average particle size to the size described in the table. The inorganic carrier "NS-20C" manufactured by TOAGOSEI CO., LTD corresponds to aluminosilicate glass.

From the above results, it was confirmed that the 2 nd metal-containing material was a particle, and the deodorizing property was further improved as compared with the case where the average particle diameter thereof was 1.5 μm or less (preferably 0.5 μm or less, more preferably 0.2 μm or less, and further preferably 0.15 μm or less).

[ example 8: preparation of composition 8 ]

The COPPER OXIDE particles (KANTO CHEMICAL co., inc. "COPPER (II) OXIDE") were dried at a low temperature under reduced pressure at 4 ℃ for 40 hours, thereby removing water. Next, the dried copper oxide particles were dispersed by diluting with water 10 times, and then wet-milled using a bead mill. The obtained dispersion was dried under reduced pressure at 50 ℃ for 5 hours, thereby preparing a CuO powder having an average particle size of 30 nm.

Particle size control was performed in the same manner as for copper (II) oxide used in composition 8, except that the polishing time and the type of filter were changed for copper (II) oxide particles used in composition 16 (example 16) described later.

In a vessel, while 150g of an aqueous dispersion (solid content concentration: 0.1% by mass) of polymer particles (NIPPON SHOKUBAI CO., manufactured by LTD. "EPOSTAR 100W", manufactured by LTD., average particle diameter: 150nm) was stirred, 0.1g of a silicate-based compound (MKC (registered trademark) silicate MS51, manufactured by Mitsubishi Chemical Corporation) was added and stirred for 20 minutes. Subsequently, 50g of an aqueous dispersion of COPPER OXIDE (COPPER (II) OXIDE "manufactured by inc., KANTO CHEMICAL co., 50) (solid content concentration 0.01 mass%: average particle diameter 30nm) having a controlled particle diameter was added to the stirred material, and the mixture was further stirred for 20 minutes, thereby obtaining a dispersion C.

The dispersion C contains copper-carrying polymer particles (corresponding to an organic material containing the 2 nd metal) as the 2 nd metal-containing material.

In the column of the present example, the average particle diameters of the copper oxide particles and the polymer particles in the copper-carrying polymer particles were replaced by the following average particle diameters: the average particle diameter obtained by the following measurement based on dynamic light scattering was measured using a dispersion of copper oxide particles alone and a dispersion of polymer particles alone.

(measurement of average particle diameter of copper oxide particle and Polymer particle)

The average particle diameter of the copper oxide particles and the polymer particles in the dispersion is measured by dynamic light scattering using a particle size distribution measuring instrument based on laser diffraction, for example.

Specifically, the measurement was performed using a dynamic light scattering measuring apparatus (Zetasizer ZS) manufactured by Marveln corporation. The following values were used for the average particle diameter: the Average value of the particle size was measured 3 times and the Average value of the values measured 3 times was measured as an Average value (Z-Average) based on the cumulative amount analysis in the manner specified in ISO 13321.

Subsequently, the obtained dispersion C was centrifuged to precipitate copper-carrying polymer particles. The copper-carrying polymer particles were separated by filtration and naturally dried under reduced pressure, thereby obtaining copper-carrying polymer particles. It was confirmed by observation with an optical microscope that the copper-supporting polymer particles had a structure in which copper oxide particles were supported on the surfaces of the polymer particles, and a coating of a silane compound obtained by condensing a silicate compound was formed on at least one region of the surfaces of the polymer particles.

The average particle diameter of the copper-carrying polymer particles was 0.6. mu.m.

As the inorganic material (1), 0.1g of zirconium phosphate having an average particle diameter of 0.3 μm was added to the obtained dispersion C and stirred, thereby obtaining a composition 8.

The zirconium phosphate corresponds to a material obtained by controlling "NS-10" manufactured by TOAGOSEI CO., LTD., Inc. to an average particle size of 0.3. mu.m.

The obtained composition 8 of example 8 contained the inorganic substance (1), the 2 nd metal-containing substance (organic substance containing the 2 nd metal), the silicate-based compound as the hydrophilic component, and the solvent.

< evaluation C >

(preparation of test sample)

The composition 8 obtained above was evaluated for its deodorizing properties according to the tests shown below.

First, a nonwoven fabric was prepared, and the composition 8 was sprayed onto the nonwoven fabric so as to be per 100cm²1g of composition 8 was attached. Subsequently, the obtained nonwoven fabric with the composition 8 was dried at 25 ℃ for 2 days, thereby producing a tape film substrate 8.

(evaluation of deodorizing ability)

10g of urine emitting ammonia odor was sprayed onto the film-attached substrate 8, and the film-attached substrate was left at room temperature. After standing, the odor was evaluated organoleptically after 1 hour and after 8 hours. The results are shown in Table 3.

Reference to evaluation

"AA": the odor was smelled only very weakly.

"A": almost no odor was smelled.

"B": smelling the odor slightly.

"C": smelling the odor slightly.

"D": smelling odor.

"E": smelling the odor strongly.

(evaluation of antibacterial Properties)

The antibacterial properties of the film-coated substrate 8 were evaluated.

For evaluation of antibacterial properties, according to JIS Z2801: 2012, the test was carried out using coliform bacteria, and the contact time with the bacterial suspension was changed to 24 hours. The antibacterial activity value after the test was measured and evaluated according to the following evaluation criteria. The results are shown in Table 3.

Reference to evaluation

"A": the antibacterial activity value is more than 2.5

"B": the antibacterial activity value is more than 1.0 and less than 2.5

"C": antibacterial activity value less than 1.0

(Membrane surface pH)

The antibacterial properties of the film-coated substrate 8 were evaluated. The evaluation method was as described above.

Examples 9 to 10: preparation of composition 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 kind and average particle diameter of the inorganic material (1) were changed to the compositions shown in Table 3.

The compositions 9 to 10 of examples 9 to 10 thus obtained contained an inorganic substance (1), a 2 nd metal-containing substance (organic substance containing the 2 nd metal), a silicate compound as a hydrophilic component, and a solvent.

Using the compositions 9 to 10 thus obtained, various evaluations were carried out in the same manner as for the composition 8. The results are shown in Table 3.

[ examples 16 and 20: preparation of compositions 16, 20 ]

Compositions 16 and 20 of examples 16 and 20 were prepared in the same manner as composition 8 of example 8, except that additives were further added in the amounts shown in table 3.

The compositions 16 and 20 obtained in examples 16 and 20 contained the inorganic substance (1), the 2 nd metal-containing substance (organic substance containing the 2 nd metal), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained compositions 16 and 20, various evaluations were performed in the same manner as in the composition 8. The results are shown in Table 3.

[ example 11: preparation of composition 11 ]

In a vessel, while stirring 367g of ethanol, 60g of pure water, 14g of a silicate compound ("MKC (registered trademark) silicate" MS51 "manufactured by Mitsubishi Chemical Corporation), 15g of aluminum chelate D (bis (ethyl acetoacetate) mono (acetylacetone) aluminum, 15g of ethanol diluted so as to have a solid content concentration of 1 mass%), 10g of a nonionic surfactant (NIHON EMULSION Co., manufactured by Ltd., EMLEX 715" manufactured by Ltd., pure water diluted so as to have a solid content concentration of 0.5 mass%), 18g of isopropyl alcohol, 3.6g of a dispersant (DISPERBYK (registered trademark) -180 "manufactured by BYK-Chemie GmbH), and silver-loaded glass particles (Fuji Ltd., manufactured by Chemical Co., Ltd.) having an average particle diameter of 0.6 μm were added in this order, ethanol dilution: solid content concentration 60 mass%) 2.4g, and stirred for 20 minutes, thereby obtaining dispersion D.

The silver-loaded glass particles in the dispersion D correspond to the inorganic material (1).

As the 2 nd metal-containing material, 0.28g of zirconium phosphate (corresponding to the inorganic substance (2)) having an average particle diameter of 0.3 μm was added to the obtained dispersion liquid D and stirred, thereby obtaining a composition 11.

The obtained composition 11 of example 11 contained the inorganic substance (1), the 2 nd metal-containing substance (inorganic substance (2)), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained composition 11, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

Examples 12 to 13: preparation of composition 12 to 13 ]

Compositions 12 to 13 of examples 12 to 13 were prepared in the same manner as composition 11 of example 11 except that the kind and average particle size of the metal content 2 were changed to the compositions shown in Table 3.

The compositions 12 to 13 of examples 12 to 13 thus obtained contained an inorganic substance (1), a 2 nd metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.

Using the compositions 12 to 13 thus obtained, various evaluations were carried out in the same manner as for the composition 8. The results are shown in Table 3.

[ example 14: preparation of composition 14 ]

A dispersion C1 was obtained in the same manner as the dispersion C except that the average particle diameter of the copper-carrying polymer particles was changed from 0.6 μm to 0.3. mu.m.

Composition 14 of example 14 was prepared in the same manner as composition 8 of example 8, except that dispersion C was changed to dispersion C1.

The obtained composition 14 of example 14 contained the inorganic substance (1), the 2 nd metal-containing substance (organic substance containing the 2 nd metal), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained composition 14, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

[ example 15: preparation of composition 15 ]

Dispersion D1 was obtained in the same manner as dispersion D except that the average particle size of the inorganic material (1) (silver-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 contained the inorganic substance (1), the 2 nd metal-containing substance (inorganic substance (2)), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained composition 15, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

[ examples 17, 18, and 21: preparation of compositions 17, 18, 21]

Compositions 17, 18 and 23 of examples 17, 18 and 21 were prepared in the same manner as composition 15 of example 15 except that additives were further added in the amounts shown in table 3.

The compositions 17, 18, and 21 of examples 17, 18, and 21 obtained contained the inorganic substance (1), the 2 nd metal-containing substance (inorganic substance (2)), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained compositions 17, 18, and 21, various evaluations were performed in the same manner as in composition 8. The results are shown in Table 3.

[ example 19: preparation of composition 19 ]

A dispersion C2 was prepared in the same manner as the metal-containing material 2 except that 0.1g of copper-carrying glass (TOAGOSEI CO., manufactured by LTD. "NS-20℃: wherein the inorganic carrier of TOAGOSEI CO., manufactured by LTD." NS-20℃ "corresponds to aluminosilicate glass.) was added to the dispersion so as to have an average particle diameter controlled to a size shown in Table 3.

The dispersion C2 contained copper-carrying glass (corresponding to the inorganic substance (2)) and copper-carrying polymer particles (corresponding to the organic substance containing the 2 nd metal) as the 2 nd metal-containing substance.

As the inorganic material (1), 0.28g of zirconium phosphate having an average particle diameter of 0.3 μm was added to the obtained dispersion C and stirred, thereby obtaining a composition 21. The obtained composition 19 of example 19 contained the inorganic substance (1), the 2 nd metal-containing substance (inorganic substance (2), organic substance containing the 2 nd metal), the silicate compound and the solvent.

Using the obtained composition 19, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

Example 22: preparation of composition 22 ]

As the metal-containing compound No. 2, 0.28g of zirconium phosphate having an average particle size of 0.3 μm and 0.1g of copper-carrying glass having an average particle size of the size shown in the table (TOAGOSEI CO., manufactured by LTD. "NS-20C"; and inorganic carrier of TOAGOSEI CO., manufactured by LTD. "NS-20℃" corresponds to aluminosilicate glass.) were added to the obtained dispersion D1 and stirred to obtain a composition 22. The obtained composition 22 of example 22 contained the inorganic substance (1), the 2 nd metal-containing substance (2 kinds of inorganic substances (2)), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained composition 22, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

[ example 23: preparation of composition 23 ]

As the 2 nd metal-containing substance, 0.28g of zirconium phosphate having an average particle size of 1.1 μm and 0.28g of copper-carrying glass having an average particle size of the size shown in the table (TOAGOSEI CO., manufactured by LTD. "NS-20C"; and inorganic carrier of TOAGOSEI CO., manufactured by LTD. "NS-20℃" corresponds to aluminosilicate glass.) were added to the obtained dispersion D1 and stirred, thereby obtaining a composition 23. The obtained composition 23 of example 23 contained the inorganic substance (1), the 2 nd metal-containing substance (2 kinds of inorganic substances (2)), the silicate-based compound as the hydrophilic component, and the solvent.

Using the obtained composition 23, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

Comparative example 4: preparation of composition R4 ]

A composition R4 of comparative example 4 was prepared in the same manner as in example 8, except that the inorganic substance (1) was not used.

Using the obtained composition R4, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

[ comparative example 5: preparation of composition R5 ]

A composition R5 of comparative example 5 was prepared in the same manner as in example 11, except that the No. 2 metal-containing substance was not used.

Using the obtained composition R5, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

Comparative example 6: preparation of composition R6 ]

A composition R6 of comparative example 6 was prepared in the same manner as in example 8, except that 0.1g of a silicate-based compound ("MKC (registered trademark) silicate" MS51 "manufactured by Mitsubishi chemical Corporation) and 200g of pure water were used in place of the dispersant C, instead of using the dispersant C.

Using the obtained composition R6, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

Comparative example 7: preparation of composition R7 ]

Composition R7 of comparative example 7 was prepared in the same manner as in example 11, except that 14g of a silicate-based compound ("MKC (registered trademark) silicate" MS51 "manufactured by Mitsubishi Chemical Corporation) and 536g of pure water were used in place of dispersant D, instead of dispersant D.

Using the obtained composition R7, various evaluations were carried out in the same manner as in composition 8. The results are shown in Table 3.

"BHT" in the table is an abbreviation for dibutylhydroxytoluene.

The "zirconium phosphate" in the table is TOAGOSEI CO., LTD. "NS-10" in which the average particle diameter is controlled to the size described in the table.

The "phosphate glass" in the table is a phosphate glass manufactured by Fuji chemical industries, ltd., which has an average particle diameter controlled to the size described in the table.

The "copper-carrying glass" in the table is a glass having an average particle diameter controlled to be the size described in the table, manufactured by ltd, "NS-20C: the inorganic carrier "NS-20C" manufactured by TOAGOSEI CO., LTD corresponds to aluminosilicate glass. ".

From the results in Table 3, it was confirmed that the films obtained from the compositions of examples 8 to 23 were excellent in antibacterial properties and deodorizing properties. In particular, it was confirmed that the deodorizing property continued for a long time.

Further, from the comparison of examples 8 to 14, it was confirmed that the deodorizing property is more excellent when the inorganic substance (1) and the 2 nd metal-containing substance are both particles and the average particle diameters of the inorganic substance (1) and the 2 nd metal-containing substance are both 0.6 μm or less (preferably 0.5 μm or less).

Further, it was confirmed from the comparison between examples 8 and 16 and 20, and between examples 15 and 17 and 21 that the deodorizing property was more excellent when citric acid was used together as an additive.

Further, from the comparison between example 8 and example 19, it was confirmed that when 2 or more kinds of metal-carrying carriers are used together as the 2 nd metal-containing substance (preferably, when the 2 nd metal-organic carrier and the 2 nd metal-inorganic carrier are used together), the deodorizing property is more excellent.

Further, from comparison between examples 15 and 22, it was confirmed that when the inorganic material (1) comprises a silver-carrying glass and the 2 nd metal-containing material comprises a copper-carrying glass, the deodorizing property is more excellent.

[ example 24: preparation of composition 24 ]

To a vessel, 38g of pure water, 0.41g of a silicate-based compound ("MKC (registered trademark) silicate" MS51 "manufactured by Mitsubishi Chemical Corporation), 1.3g of aluminum chelate D (bis (ethyl acetoacetate) mono (acetylacetone) aluminum, ethanol dilution: solid content concentration 1 mass%), 0.8g of an anionic surfactant (NIHON EMULSION Co., Ltd.," EMLEX 715 "manufactured by Ltd., pure water dilution: solid content concentration 0.5 mass%), 2.7g of isopropyl alcohol, 1g of an inorganic substance (1) (corresponding to a silver-carrying glass having an average particle diameter of 1.1 μm, manufactured by Fuji Industries, Ltd., Chemical industry" 103 "Chemical industry Co., Ltd.),103" 1.1 μm was added in this order while stirring 52g of ethanol, the inorganic carrier "Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd. corresponds to phosphate glass. ) Ethanol/water solvent dilution: solid content concentration 25.3 mass%), 0.039g, a dispersant (DISPERBYK (registered trademark) -180, manufactured by BYK) 0.04g, ethanol 1.4g, and a 2 nd metal content (copper-carrying glass (corresponding to a glass having an average particle size of 3.1 μm, manufactured by TOAGOSEI co., ltd. "NS-20C," manufactured by ltd., having an average particle size of 3.1 μm; inorganic carrier, manufactured by TOAGOSEI co., ltd. "NS-20C," manufactured by ltd., corresponding to aluminum silicate glass): solid content concentration 100 mass%) 0.489g, and stirred for 20 minutes, thereby obtaining composition 24.

The composition 24 of example 24 thus obtained contained an inorganic substance (1), a 2 nd metal-containing substance (inorganic substance (2)), a silicate compound as a hydrophilic component, and a solvent.

Using the obtained composition 24, various evaluations were carried out according to the following < evaluation D >.

The following evaluation D was set to more stringent evaluation conditions than the above evaluations a to C.

< evaluation D >

(preparation of test sample)

The composition 24 obtained above was evaluated for its deodorizing properties according to the tests shown below.

First, a nonwoven fabric is prepared, and the composition 24 is sprayed to the nonwoven fabric so that the nonwoven fabric is per 100cm²0.06g of composition 24 was adhered. Subsequently, the obtained nonwoven fabric with the composition 24 was dried at 25 ℃ for 2 days, thereby producing a film-attached substrate 24.

(evaluation of deodorizing ability)

10g of urine emitting ammonia odor was sprayed onto the film-attached substrate 24, and the substrate was left at room temperature. After standing, the odor was evaluated organoleptically after 1 hour and after 8 hours. The results are shown in Table 4.

Reference to evaluation

"AA": the odor was smelled only very weakly.

"A": almost no odor was smelled.

"B": smelling the odor slightly.

"C": smelling the odor slightly.

"D": smelling odor.

(evaluation of antibacterial Properties)

The antibacterial properties of the film-coated substrate 24 were evaluated.

For evaluation of antibacterial properties, according to JIS Z2801: 2012, the test was carried out using coliform bacteria, and the contact time with the bacterial suspension was changed to 24 hours. The antibacterial activity value after the test was measured and evaluated according to the following evaluation criteria. The results are shown in Table 4.

Reference to evaluation

"A": the antibacterial activity value is more than 2.5

"B": the antibacterial activity value is more than 1.0 and less than 2.5

"C": antibacterial activity value less than 1.0

Examples 25 to 30: preparation of composition 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 metal-containing substance 2 were adjusted to the amounts shown in table 4. The results are shown in Table 4.

Examples 31 to 37: preparation of composition 31 to 37 ]

Compositions 31 to 37 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle size of the inorganic material (1) was adjusted to the size shown in table 4. The results are shown in Table 4.

[ examples 38 to 44: preparation of composition 38 to 44

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

Examples 45 to 51: preparation of composition 45 to 51 ]

Compositions 45 to 51 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameter of the metal content 2 was adjusted to the size shown in table 4. The results are shown in Table 4.

Examples 52 to 58: preparation of composition 52 to 58

Compositions 52 to 58 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameter of the metal content 2 was adjusted to the size shown in table 4. The results are shown in Table 4.

Examples 59 to 65: preparation of composition 59 to 65 ]

Compositions 59 to 65 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameter of the 2 nd metal-containing material was adjusted to the size shown in table 4. The results are shown in Table 4.

Examples 66 to 72: preparation of composition 66 to 72 ]

Compositions 66 to 72 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameters of the inorganic material (1) and the metal content 2 were adjusted to the sizes shown in table 4. The results are shown in Table 4.

Examples 73 to 79: preparation of composition 73 to 79 ]

Compositions 73 to 79 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameters of the inorganic material (1) and the metal content 2 were adjusted to the sizes shown in table 4. The results are shown in Table 4.

Examples 80 to 86: preparation of composition 80 to 86 ]

Compositions 80 to 86 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameters of the inorganic material (1) and the metal content 2 were adjusted to the sizes shown in table 4. The results are shown in Table 4.

Examples 87 to 93: preparation of composition 87-93 ]

Compositions 87 to 93 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameters of the inorganic material (1) and the metal-containing material 2 were adjusted to the sizes shown in table 4. The results are shown in Table 4.

Examples 94 to 100: preparation of composition 94 to 100 ]

Compositions 94 to 100 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameters of the inorganic material (1) and the metal content 2 were adjusted to the sizes shown in table 4. The results are shown in Table 4.

Examples 101 to 107: preparation of compositions 101 to 107 ]

Compositions 101 to 107 were prepared and evaluated in the same manner as in examples 24 to 30, except that the kind and content of the inorganic substance (1) and the average particle diameter of the 2 nd metal-containing substance were changed to those shown in table 4. The results are shown in Table 4.

The inorganic material (1) used in examples 101 to 107 was a silver-loaded zeolite (Nakamura Choukou Co., Ltd., "Zeoal 4A" by Ltd., water dilution: solid content concentration 19 mass%) whose average particle diameter was controlled to 0.3. mu.m.

Examples 108 to 114: preparation of composition 108 to 114

Compositions 108 to 114 were prepared and evaluated in the same manner as in examples 24 to 30, except that the type and content of the inorganic substance (1) were changed to those shown in table 4 and the content and average particle size of the inorganic substance (2) were changed to those shown in table 4. The results are shown in Table 4.

The inorganic material (1) used in examples 108 to 114 was silver-loaded zirconium phosphate (TOAGOSEI co., ltd, "Novalon AG 300", solid content concentration 100 mass%) whose average particle size was controlled to 1.0 μm.

Examples 115 to 121: preparation of composition 115 to 121 ]

Compositions 115 to 121 were prepared and evaluated in the same manner as in examples 31 to 37, except that the ethanol concentration was adjusted to the amount shown in table 4. The results are shown in Table 4.

Examples 122 to 128: preparation of composition 122-128 ]

Compositions 122 to 128 were prepared and evaluated in the same manner as in examples 87 to 93, except that the ethanol concentration was adjusted to the amount shown in table 4. The results are shown in Table 4.

Example 129 to 135: preparation of composition 129 to 135 ]

Compositions 129 to 135 were prepared and evaluated in the same manner as in examples 101 to 107, except that the ethanol concentration was adjusted to the amount shown in table 4. The results are shown in Table 4.

[ examples 136 to 142: preparation of composition 136 to 142

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

[ examples 143 to 149: preparation of compositions 143 to 149 ]

Compositions 143 to 149 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle size of the inorganic material (1) was adjusted to the size shown in table 4 and the type and content of the 2 nd metal content were adjusted to the amounts shown in table 4. The results are shown in Table 4.

The metal-containing substance 2 used in examples 143 to 149 was copper-carrying polymer particles (corresponding to an organic substance containing metal-2) having an average particle diameter of 0.6. mu.m.

The copper-carrying polymer particles were produced by the following method and used.

(copper-carrying Polymer particles)

In a vessel, while 150g of an aqueous dispersion (solid content concentration: 0.1% by mass) of polymer particles (NIPPON SHOKUBAI CO., manufactured by LTD. "EPOSTAR 100W", manufactured by LTD., average particle diameter: 150nm) was stirred, 0.1g of a silicate-based compound (MKC (registered trademark) silicate MS51, manufactured by Mitsubishi Chemical Corporation) was added and stirred for 20 minutes. Subsequently, 50g of an aqueous dispersion of COPPER OXIDE (COPPER (II) OXIDE "manufactured by inc., KANTO CHEMICAL co., 50) (solid content concentration 0.01 mass%: average particle diameter 30nm) having a controlled particle diameter was added to the stirred material, and the mixture was further stirred for 20 minutes, thereby obtaining a dispersion F.

Subsequently, the obtained dispersion liquid F was centrifuged to precipitate copper-carrying polymer particles. The copper-carrying polymer particles were separated by filtration and naturally dried under reduced pressure, thereby obtaining copper-carrying polymer particles. It was confirmed by observation with an optical microscope that the copper-supporting polymer particles had a structure in which copper oxide particles were supported on the surfaces of the polymer particles, and a coating of a silane compound obtained by condensing a silicate compound was formed on at least one region of the surfaces of the polymer particles. Further, by adjusting the dispersion time, copper-carrying polymer particles having 2 sizes, i.e., an average particle diameter of 0.6 μm and an average particle diameter of 0.3 μm, were produced.

Examples 150 to 156: preparation of composition 150 to 156 ]

Compositions 150 to 156 were 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 shown in table 4 and the type and content of the 2 nd metal content were adjusted to the amounts shown in table 4. The results are shown in Table 4.

The metal-containing substance 2 used in examples 150 to 156 was copper-carrying polymer particles (corresponding to an organic substance containing metal-2) having an average particle diameter of 0.3. mu.m.

Examples 157 to 163: preparation of composition 157 to 163

Compositions 157 to 163 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameter of the inorganic substance (1) was adjusted to the size shown in table 4 and the type and content of the 2 nd metal content were adjusted to the amounts shown in table 4. The results are shown in Table 4.

The metal-containing material No. 2 used in examples 157 to 163 was copper oxide particles (corresponding to the inorganic material (2)) having an average particle diameter of 0.03. mu.m.

Examples 164 to 170: preparation of composition 164 to 170 ]

Compositions 164 to 170 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameter of the inorganic substance (1) was adjusted to the size shown in table 4 and the type and content of the 2 nd metal content were adjusted to the amounts shown in table 4. The results are shown in Table 4.

The metal-containing substance 2 used in examples 164 to 170 was copper-carrying polymer particles (corresponding to an organic substance containing the metal-containing substance 2) having an average particle diameter of 0.6. mu.m.

Examples 171 to 177: preparation of composition 171 to 177 ]

Compositions 171 to 177 were prepared and evaluated in the same manner as in examples 24 to 30, except that the average particle diameter of the inorganic substance (1) was adjusted to the size shown in table 4 and the type and content of the 2 nd metal content were adjusted to the amounts shown in table 4. The results are shown in Table 4.

The metal-containing substance 2 used in examples 171 to 177 was copper-carrying polymer particles (corresponding to an organic substance containing metal-2) having an average particle diameter of 0.3. mu.m.

Examples 178 to 184: preparation of compositions 178 to 184 ]

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

Examples 185 to 191: preparation of composition 185 to 191

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

Examples 192 to 198: preparation of composition 192 to 198

Compositions 192 to 198 were prepared and evaluated in the same manner as in examples 94 to 100, except that the content of the dispersant was adjusted to the amount shown in table 4. The results are shown in Table 4.

Examples 199 to 205: preparation of composition 199 to 205 ]

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

Examples 206 to 212: preparation of composition 206-212 ]

Compositions 206 to 212 were prepared and evaluated in the same manner as in examples 31 to 37, except that zirconium phosphate (TOAGOSEI co., ltd. "NS-10" manufactured by ltd.) having an average particle diameter of 0.8 μm was further added as the metal content 2 in an amount shown in table 4, and the ethanol concentration was adjusted to the concentration shown in table 4. The results are shown in Table 4.

Examples 213 to 219: preparation of composition 213 to 219 ]

Compositions 213 to 219 were prepared and evaluated in the same manner as in examples 87 to 93 except that zirconium phosphate (TOAGOSEI co., ltd. "NS-10") having an average particle diameter of 0.8 μm was further added as the metal content of the 2 nd metal in the amount shown in table 4. The results are shown in Table 4.

Example 220: preparation of composition 220 ]

Composition 220 was prepared and evaluated in the same manner as in example 219, except that aluminum silicate (toagasei co., ltd. "NS-20") having an average particle size of 0.15 μm was used as metal-containing material 2, and zirconium phosphate (toagasei co., ltd. "NS-10") having an average particle size of 0.8 μm was not added as metal-containing material 2. 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 no 2 nd metal content was blended. The results are shown in Table 4.

Comparative example 9: preparation of composition R9 ]

A composition R9 was prepared and evaluated in the same manner as in example 26, except that no 2 nd metal content was blended. The results are shown in Table 4.

Comparative example 10: preparation of composition R10 ]

A composition R10 was prepared and evaluated in the same manner as in example 44, except that no 2 nd metal content was 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 in example 40, except that no 2 nd metal content was blended. The results are shown in Table 4.

Comparative example 12: preparation of composition R12 ]

A composition R12 was prepared and evaluated in the same manner as in example 103, except that the No. 2 metal content 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 no 2 nd metal content was added. The results are shown in Table 4.

Comparative examples 14 and 15: preparation of compositions R14, R15 ]

Compositions R14 and R19 were prepared and evaluated in the same manner as in example 24 and example 26 except that no silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd.) was used. The results are shown in Table 4.

Comparative examples 16 and 17: preparation of compositions R16, R17 ]

Compositions R16 and R17 were prepared and evaluated in the same manner as in example 52 and example 54 except that silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd.) was not blended. The results are shown in Table 4.

Comparative examples 18 and 19: preparation of compositions R18, R19 ]

Compositions R18 and R19 were prepared and evaluated in the same manner as in examples 88 and 89 except that no silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji chemical industries, Ltd.) was used. The results are shown in Table 4.

Comparative examples 20 and 21: preparation of compositions R20, R21 ]

Compositions R20 and R21 were prepared and evaluated in the same manner as in example 143 and example 145 except that silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd.) was not blended. The results are shown in Table 4.

Comparative examples 22 and 23: preparation of compositions R22, R23 ]

Compositions R22 and R23 were prepared and evaluated in the same manner as in example 150 and example 152 except that no silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd.) was used. The results are shown in Table 4.

Comparative examples 24 and 25: preparation of compositions R24, R25 ]

Compositions R24 and R25 were prepared and evaluated in the same manner as in example 157 and example 159 except that no silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd.) was used. The results are shown in Table 4.

Comparative example 26: preparation of composition R26 ]

A composition R26 was prepared and evaluated in the same manner as in example 206 except that silver-carrying glass ("Bactelite MP-103 DV" manufactured by Fuji Chemical Industries, Ltd.) and copper-carrying glass ("NS-20C" manufactured by LTD.) were not blended. The results are shown in Table 4.

Comparative example 27: preparation of composition R27 ]

Composition R27 was prepared and evaluated in the same manner as in comparative example 26 except that aluminum silicate was blended (average particle size was controlled to TOAGOSEI co., ltd. "NS-20" manufactured by ltd., in place of zirconium phosphate), and the results are shown in table 4.

Table 4 is shown below.

In the table, "silver-carrying glass" is "Bactelite MP-103DV (solid content: 25.3% by mass)" manufactured by Fuji chemical industries, Ltd. Further, the inorganic carrier "Bactelite MP-103 DV" manufactured by Fuji chemical industries, Ltd. corresponds to phosphate glass.

In the table, "copper-carrying glass" means TOAGOSEI CO., LTD. "NS-20C" (solid content 100 mass%) 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 aluminosilicate glass.

In the table, "silver-carrying zeolite" is Nakamura choukoukou co., ltd. "Zeoal 4A" (solid content 19%) whose average particle diameter is controlled to the size described in the table.

In the table, "silver-loaded zirconium phosphate" is TOAGOSEI co., ltd "Novalon AG 300" (100 mass% solid content), which has an average particle size controlled to the size described in the table.

In the table, "copper oxide" is copper oxide (solid content 100 mass%) whose average particle size is controlled to the size shown in the table.

The "zirconium phosphate" in the table is "NS-10" (100 mass% of solid content) manufactured by ltd.

The "aluminum silicate" in the table is TOAGOSEI co, ltd "NS-20" (solid content 100 mass%) whose average particle size is controlled to the size described in the table.

From the results of examples 24 to 100, it was confirmed that the deodorizing property of the formed film was more excellent in the case where the average particle diameters of the silver-carrying glass and the copper-carrying glass were 1.2 μm or less.

Among them, it was confirmed from the results of examples 52 to 72 that when either one of the silver-carrying glass and the copper-carrying glass had an average particle size of 1.2 μm or less and the other had an average particle size of 0.9 μm or less, the formed film was more excellent in deodorizing property. Among these, it was confirmed that the deodorizing property of the formed film was more excellent in the case where either one of the silver-carrying glass and the copper-carrying glass had an average particle size of 1.2 μm or less and the other had an average particle size of 0.6 μm or less, or both of the silver-carrying glass and the copper-carrying glass had an average particle size of 0.9 μm or less.

Among them, from the results of examples 73 to 93, it was confirmed that the films formed when the average particle diameters of the silver-carrying glass and the copper-carrying glass were both 0.5 μm or less (preferably, when the average particle diameter of either one of the silver-carrying glass and the copper-carrying glass was 0.5 μm or less and the average particle diameter of the other was 0.3 μm or less) were more excellent in the deodorizing property.

Among them, it was confirmed from the results of examples 94 to 100 that the deodorizing property of the formed film tends to be more excellent in the case where the average particle diameter of the silver-carrying glass and the copper-carrying glass is 0.3 μm or less.

Further, from comparison of examples 94 to 100 with examples 101 to 107, it was confirmed that when the inorganic carrier of the inorganic substance (1) is glass, the deodorizing property of the formed film is more excellent.

Further, from the comparison between examples 24 to 100 and examples 143 to 177, it was confirmed that the deodorizing property of the formed film tends to be more excellent in the case where the inorganic substance (1) is a silver-carrying glass and the 2 nd metal-containing substance is a copper-carrying glass.

Further, it was confirmed from the comparison of examples 31 to 37 with examples 115 to 121 and the comparison of examples 87 to 93 with examples 122 to 128 that the deodorizing property of the formed film tends to be more excellent in the case where the ethanol concentration in the composition is 45 mass% or less.

On the other hand, from the comparison of examples 101 to 107 with examples 129 to 135 and the comparison of examples 116 to 114 with examples 136 to 142, it was confirmed that the deodorizing property of the formed film tends to be more excellent when the ethanol concentration in the composition is 5 mass% or more.

Further, from comparison between examples 94 to 100 and examples 192 to 205, it was confirmed that when the content of the dispersant in the composition was 15% by mass or more based on the total solid content of the composition (corresponding to examples 192 to 205), the deodorizing property of the formed film tended to be more excellent.

Further, it was confirmed from comparison of examples 178 to 191 and examples 94 to 100 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]

In a vessel, while 150g of an aqueous dispersion (solid content concentration: 0.1% by mass) of polymer particles (NIPPON SHOKUBAI CO., manufactured by LTD. "EPOSTAR 100W", manufactured by LTD., average particle diameter: 150nm) was stirred, 0.1g of a silicate-based compound (MKC (registered trademark) silicate MS51, manufactured by Mitsubishi Chemical Corporation) was added and stirred for 20 minutes. Subsequently, 50G of an aqueous dispersion of COPPER OXIDE (COPPER (II) OXIDE "manufactured by inc., KANTO CHEMICAL co., 50) (solid content concentration 0.01 mass%: average particle diameter 30nm) having a controlled particle diameter was added to the stirred material, and the mixture was further stirred for 20 minutes, thereby obtaining a dispersion G.

Subsequently, the obtained dispersion G was centrifuged to precipitate copper-carrying polymer particles. The copper-carrying polymer particles were separated by filtration and naturally dried under reduced pressure, thereby obtaining copper-carrying polymer particles. It was confirmed by observation with an optical microscope that the copper-supporting polymer particles had a structure in which copper oxide particles were supported on the surfaces of the polymer particles, and a coating of a silane compound obtained by condensing a silicate compound was formed on at least one region of the surfaces of the polymer particles.

As the 1 st metal inorganic carrier, 0.1G of a copper-carrying glass (TOAGOSEI CO., manufactured by LTD. "NS-20C": further, the inorganic carrier of TOAGOSEI CO., manufactured by LTD. "NS-20C") was added to the obtained dispersion G and stirred, thereby obtaining a reference composition 1.

The obtained reference composition 1 of reference example 1 contained the 1 st metal organic carrier, the 2 nd metal inorganic carrier, a silicate-based compound as a hydrophilic component, and a solvent.

(average particle diameter of No. 1 Metal inorganic Carrier, No. 1 Metal organic Carrier)

The average particle diameters of the 1 st metal inorganic carrier and the 1 st metal organic carrier were measured by observation with an electron microscope. The specific measurement method is as described above.

The obtained reference composition 1 of reference example 1 was evaluated in the same manner as in example 1. The results are shown in Table 5.

[ reference example 1]

Reference composition 2 of reference example 2 was prepared in the same manner as reference composition 1 of reference example 1, except that the MKC silicate MS51 was not used.

The "copper-carrying glass" in Table 5 is TOAGOSEICO, LTD, NS-20C, in which the average particle diameter is controlled to the size shown in the table. The inorganic carrier manufactured by TOAGOSEI CO., LTD. "NS-20C" is equivalent to aluminum silicate.

[ Table 21]

Claims

1. A composition comprising:

inorganic substances containing a 1 st metal;

a solvent.

2. The composition of claim 1, wherein,

the 1 st metal-containing inorganic substance is at least 1 selected from the group consisting of a simple substance of the 1 st metal, an oxide of the 1 st metal, and a metal-supporting inorganic support having an inorganic support and the 1 st metal supported on the inorganic support.

3. The composition of claim 1, wherein,

the 2 nd metal-containing inorganic substance is at least 1 selected from the group consisting of an elemental substance of the 2 nd metal, an oxide of the 2 nd metal, and a metal-supporting inorganic support having an inorganic support and the 2 nd metal supported on the inorganic support.

4. The composition according to any one of claims 1 to 3,

the component containing the 2 nd metal is the inorganic substance containing the 2 nd metal.

5. The composition according to claim 4, wherein,

the 1 st metal-containing inorganic substance and the 2 nd metal-containing inorganic substance are particles,

either one of the 1 st metal-containing inorganic substance and the 2 nd metal-containing inorganic substance has an average particle diameter of 1.2 μm or less and the other has an average particle diameter of 0.6 μm or less; or the average particle diameters of the 1 st metal-containing inorganic substance and the 2 nd metal-containing inorganic substance are both 0.9 [ mu ] m or less.

6. The composition according to any one of claims 1 to 5,

the 1 st metal is silver and the 2 nd metal is copper.

7. The composition according to any one of claims 1 to 6,

the 1 st metal-containing inorganic material is a silver-carrying inorganic carrier having a 1 st inorganic carrier and silver carried on the 1 st inorganic carrier.

8. The composition according to any one of claims 1 to 7,

the 2 nd metal-containing inorganic substance is a copper-carrying inorganic carrier having a 2 nd inorganic carrier and copper carried on the 2 nd inorganic carrier.

9. The composition of claim 7, wherein,

the 1 st inorganic carrier is glass.

10. The composition of claim 8, wherein,

the 2 nd inorganic carrier is glass.

11. The composition according to any one of claims 4 to 6,

the metal-1 containing inorganic material is a silver-loaded glass having glass and silver supported on the glass, and the metal-2 containing inorganic material is a copper-loaded glass having glass and copper supported on the glass.

12. The composition according to any one of claims 1 to 11,

the composition further comprises: a hydrophilic component selected from the group consisting of hydrophilic adhesive precursors and hydrophilic adhesives.

13. The composition of claim 12, wherein,

the hydrophilic component contains: at least 1 selected from the group consisting of silicate compounds, monomers having hydrophilic groups, and polymers having hydrophilic groups.

14. A film, comprising:

inorganic substances containing a 1 st metal;

at least 1 metal-2-containing component selected from the group consisting of an inorganic material containing a metal-2 different from the metal-1 and an organic material containing the metal-2.

15. The film according to claim 14, wherein,

16. The film according to claim 14, wherein,

17. The film according to any one of claims 14 to 16,

18. The film according to claim 17, wherein,

19. The film according to any one of claims 14 to 18,

the 1 st metal is silver and the 2 nd metal is copper.

20. The film according to any one of claims 14 to 19,

21. The film according to any one of claims 14 to 20,

22. The film according to claim 20, wherein,

the 1 st inorganic carrier is glass.

23. The film according to claim 21, wherein,

the 2 nd inorganic carrier is glass.

24. The film according to any one of claims 17 to 19,

25. The membrane of any one of claims 14 to 24, further comprising a hydrophilic binder.

26. The film according to claim 25, wherein,

the hydrophilic binder is at least 1 selected from the group consisting of a hydrolysate of a compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, or the hydrophilic binder is a hydrophilic polymer.

27. A filmed substrate having a substrate and the film of any one of claims 14 to 26.

28. A method of manufacturing a filmed substrate, comprising:

a step of applying the composition according to any one of claims 1 to 13 containing a hydrophilic adhesive precursor to the surface of a substrate to form a composition layer; and

a step of curing the composition layer to obtain a film.

29. A method of manufacturing a filmed substrate, comprising:

a process for forming a film by applying the composition according to any one of claims 1 to 13 containing a hydrophilic binder to the surface of a substrate.

30. A modified substrate having:

a base material,

An inorganic material containing a 1 st metal and at least 1 metal-containing component selected from the group consisting of an inorganic material containing a 2 nd metal different from the 1 st metal and an organic material containing the 2 nd metal, which are disposed on or in the substrate.

31. A modified substrate having:

a base material,

An inorganic material containing a 1 st metal and at least 1 type of a 2 nd metal-containing component selected from the group consisting of an inorganic material containing a 2 nd metal different from the 1 st metal and an organic material containing the 2 nd metal, which are disposed on or in the substrate,

A hydrophilic adhesive.

32. The modified substrate of claim 30 or 31, wherein,

33. The modified substrate of claim 30 or 31, wherein,

34. The modified substrate of any one of claims 30-33, wherein,

35. The modified substrate of claim 34, wherein,

36. The modified substrate of any one of claims 30-35, wherein,

the 1 st metal is silver and the 2 nd metal is copper.

37. The modified substrate of any one of claims 30-36, wherein,

38. The modified substrate of any one of claims 30-37, wherein,

39. The modified substrate of claim 37, wherein,

the 1 st inorganic carrier is glass.

40. The modified substrate of claim 38, wherein,

the 2 nd inorganic carrier is glass.

41. The modified substrate of any one of claims 34-36, wherein,