JP6656278B2 - Antibacterial deodorizing sheet and antibacterial deodorizing method - Google Patents

Description

  The present invention relates to an antibacterial deodorizing sheet and an antibacterial deodorizing method.

  Due to the recent rise in living standards and health orientation, thorough hygiene management and comfort are required in various spaces where people enter and leave, such as living spaces, workplaces, shops, customer facilities, and public facilities. It is becoming strongly required. From the viewpoints of hygiene management and comfort, antibacterial activities such as deodorization such as removal of odors and suppression or removal of propagation of various fungi are achieved in various spaces.

  As an antibacterial deodorant having a deodorizing action and an antibacterial action, chlorine dioxide gas having a strong oxidizing power is known. However, while chlorine dioxide gas exerts an excellent antibacterial and deodorizing effect, when it exceeds a certain concentration, it may corrode metal substances or adversely affect the human body (respiratory disorders, etc.).

  Therefore, Patent Document 1 proposes an antibacterial deodorizing material and an antibacterial deodorizing method that can perform antibacterial deodorization by gradually releasing chlorine dioxide gas. Specifically, the chlorite compound is adsorbed on a powdery base material which is inert and oxidation-resistant to the chlorite compound, and the powdery base material and the powdery non-volatile acid substance And an antibacterial deodorant characterized by being mixed with a container having air permeability and water permeability.

JP 2012-161493 A

  However, the antibacterial deodorizing method of Patent Literature 1 is a mechanism of generating chlorine dioxide gas by reacting moisture in the air that has passed through a water-permeable container with a chlorite compound and a nonvolatile acidic substance. In terms of the generation of chlorine dioxide gas, there is still concern about metal corrosion and its effect on the human body.

  By the way, among deodorization and antibacterial in the above-mentioned various spaces, treatment of dead bodies may become a big problem in the future. With the aging of society rapidly progressing, it is expected that the deaths of the elderly at the same time will exceed the processing limit of crematoriums, and the period from death to cremation of the body will be prolonged It is feared that.

  It usually takes several days from death to cremation of the body. During that time, odor (dead odor) due to the decay of the corpse is generated, and bacteria grow. In order to suppress these even a little, a cold insulator such as dry ice is used. However, such a processing method using a cold insulator requires continuous replacement and replenishment for several days for preserving the corpse, which is troublesome. In addition, when dry ice is used, it is not environmentally preferable because it promotes global warming.

  Then, from the viewpoint of the treatment of dead bodies, it can be said that antibacterial deodorants capable of removing odors such as dead odors and exhibiting an antibacterial action against rot well will be more strongly demanded in the future.

  In addition, such an antibacterial deodorant, for example, in a sheet form is convenient in handling. In the case of forming a sheet, a method of supporting an antibacterial deodorant on a substrate can be considered. However, if the antibacterial deodorant drops off during use, the use effect may be reduced or the surroundings may be stained, which may cause problems.

  The present invention has been made in view of the above, and has an antibacterial deodorizing sheet that removes odor while exhibiting an antibacterial effect well, and that an antibacterial deodorant is hard to fall off, and an antibacterial deodorizing method using the antibacterial deodorizing sheet. The purpose is to provide.

As a result of intensive studies to solve the above problems, the present inventors have found that providing an antibacterial deodorant-containing resin region containing an antibacterial deodorant and a water-insoluble binder resin on at least one surface side of the nonwoven fabric sheet removes odor. The present inventors have found that an antibacterial deodorizing sheet capable of exhibiting an antibacterial action favorably and in which an antibacterial deodorizing agent is hardly removed can be obtained.
That is, the present invention is as follows.

[1] An antibacterial deodorizing sheet including a nonwoven fabric sheet, an antibacterial deodorant, and a water-insoluble binder resin, wherein the antibacterial deodorant and the water-insoluble binder resin are provided on at least one surface side of the nonwoven fabric sheet. An antibacterial deodorizing sheet having an antibacterial deodorant-containing resin region containing:
[2] The antibacterial deodorizing sheet according to [1], wherein the water-insoluble binder resin is a vinyl acetate resin.
[3] The antibacterial deodorizing sheet according to [1] or [2], wherein a mixing ratio of the water-insoluble binder resin to 100 parts by mass of the antibacterial deodorant is 30 to 600 parts by mass.
[4] The antibacterial deodorizing sheet according to any one of [1] to [3], wherein the antibacterial deodorizing agent includes an alkaline powder whose aqueous solution or dispersion has a pH of 12 or more, and an inorganic silica-based powder.
[5] The antibacterial deodorizing sheet according to [4], wherein the content of the alkaline powder is 10 to 90% by mass based on the total of the alkaline powder and the inorganic silica-based powder.
[6] The antibacterial deodorizing sheet according to [4] or [5], wherein the alkaline powder is slaked lime powder and / or dolomite powder.
[7] The antibacterial deodorizing sheet according to any one of [4] to [6], wherein the inorganic silica-based powder is an inorganic silica-based acidic powder whose aqueous solution or dispersion has a pH of 6 or less.
[8] An antibacterial deodorizing method in which the antibacterial deodorizing sheet according to any one of [1] to [7] is disposed at and / or in the vicinity of an odor source.
[9] The antibacterial deodorizing method according to [8], wherein the odor is a putrefaction gas and includes an ammonia gas and a hydrogen sulfide gas.
[10] The antibacterial deodorizing method according to [9], further including acetic acid gas as the putrefaction gas.

  ADVANTAGE OF THE INVENTION According to this invention, the antibacterial deodorizing sheet which removes an odor while exhibiting an antibacterial effect well, and which an antibacterial deodorant is hard to fall off, and an antibacterial deodorizing method using the said antibacterial deodorizing sheet can be provided.

  Hereinafter, one embodiment (the present embodiment) of the present invention will be described in detail, but the present invention is not limited thereto.

[1] Antibacterial deodorizing sheet The antibacterial deodorizing sheet of the present embodiment includes a nonwoven fabric sheet, an antibacterial deodorant, and a water-insoluble binder resin. The nonwoven fabric sheet has an antibacterial deodorant-containing resin region including an antibacterial deodorant and a water-insoluble binder resin on at least one surface side.

  With such a configuration, it is possible to obtain an antibacterial deodorizing sheet that removes an odor while exhibiting an antibacterial action well and that is hard to remove an antibacterial deodorant.

  As a configuration having an antibacterial deodorant-containing resin region containing an antibacterial deodorant and a water-insoluble binder resin on one surface side of the nonwoven fabric sheet, for example, at least the entire front surface and the back surface of the nonwoven fabric sheet, or Antimicrobial deodorant-containing resin regions are formed scatteredly on the surface. When the antibacterial deodorant-containing resin region is formed sporadically, the fibers constituting the nonwoven fabric sheet are exposed on the surface. In addition, an antimicrobial deodorant-containing resin region may be provided on both surfaces of the nonwoven fabric sheet.

  The antimicrobial deodorant-containing resin region includes a case where a layer (sometimes referred to as an “antimicrobial deodorant-containing resin layer”) is formed on the front surface or the back surface of the nonwoven fabric sheet. That is, at least a part of the antibacterial deodorizing sheet surface may be uneven due to the antibacterial deodorant-containing resin region.

  Further, in this embodiment, the antibacterial deodorant is immobilized in the antibacterial deodorant-containing resin region and the antibacterial deodorant-containing resin layer of the nonwoven fabric sheet by the water-insoluble binder resin. By using a water-insoluble binder resin, for example, an antibacterial deodorant can be more strongly immobilized than using a water-soluble binder resin. Also, when using a water-soluble binder resin, there is a concern that the surface will be tacky when it comes into contact with moisture, and there is a concern that the antibacterial deodorant will easily fall off due to friction, but this is not the case with a water-insoluble binder resin. The antibacterial deodorant can be stably immobilized.

  Here, the “water-insoluble binder resin” refers to a binder resin that can immobilize the antibacterial deodorant when the antibacterial deodorant-containing resin region is formed and is substantially insoluble in water. In addition, "substantially does not dissolve" specifically refers to a state where precipitation is visually confirmed when 1 g of the resin is added to 100 g of water and stirred at 25 ° C. for 24 hours.

Examples of the water-insoluble binder resin include a vinyl acetate resin, a polyurethane resin, an acrylic resin, a polyester resin, an epoxy resin, and a vinyl chloride resin. Here, “vinyl acetate resin” refers to a copolymer obtained by copolymerizing vinyl acetate resin, vinyl acetate, and other monomers copolymerizable with vinyl acetate (for example, vinyl acetate-acrylic copolymer). United resin). As the water-insoluble binder resin, a vinyl acetate resin or a polyurethane resin is preferable, and a vinyl acetate resin is more preferable.
In many cases, those dissolved in a solvent other than water such as toluene, methanol, ethanol, and ethyl acetate are used.

  The mixing ratio of the binder resin to 100 parts by mass of the antibacterial deodorant is preferably from 25 to 600 parts by mass, more preferably from 30 to 600 parts by mass, and still more preferably from 30 to 550 parts by mass. When the compounding ratio is 25 to 600 parts by mass, the antibacterial deodorant can be satisfactorily immobilized and the antibacterial deodorant can be prevented from falling off.

  It is preferable that the antibacterial deodorant in the present embodiment includes an alkaline powder (hereinafter, may be simply referred to as “alkaline powder”) having an aqueous solution or dispersion having a pH of 12 or more, and an inorganic silica-based powder.

  For example, when raw material is putrefactive, odorous gases such as ammonia gas and hydrogen sulfide gas are generated. Although there are means to remove each of them separately by adsorption, it is difficult to remove them at the same time because they are alkaline and acidic, respectively. In addition, since bacteria proliferate by decay, if this can be simultaneously antibacterial, it is very significant from the viewpoint of hygiene management and comfort. However, no effective technology has been found which can remove odorous gas including ammonia gas and hydrogen sulfide gas and can also realize antibacterial.

The present inventor has found that an alkaline odor supplements an acidic odor such as hydrogen sulfide gas, an inorganic silica-based powder supplements an alkaline odor such as ammonia gas, and that these can also realize antibacterial effects. . There are many unclear points about mechanisms that can also exert antibacterial action with these powders, but probably the strong alkaline property of the alkaline powder is manifested by the moisture attached or adsorbed on the inorganic silica-based powder coming into contact with the surface of the alkaline powder. It is presumed that the antibacterial effect is improved and an odor removing effect is obtained together with an excellent antibacterial effect.
The antibacterial deodorant will be described in detail below.

(Alkaline powder)
The alkaline powder is a powder having a pH of 12 or more when dissolved or dispersed by stirring for about 3 minutes and adding 10 g of the alkaline powder to 100 ml of pure water, and examples thereof include slaked lime, quicklime, and dolomite compound.
Among the above, slaked lime powder and / or dolomite-based compounds (particularly, dolomite hydroxide) are preferred from the viewpoint of cost and handleability.

Here, the dolomite-based compound (also referred to as “dolomite-based powder”) is a compound derived from dolomite, for example, light-burned dolomite, hydroxide dolomite, and the like. Dolomite is calcite. calcium carbonate referred to as (CaCO _3), and magnesium carbonate (MgCO ₃₎ called magnesite (magnesite), ideally 1: 1 double salt. In terms of composition, this is a substance located between calcite and magnesite. When dolomite is heated under relatively mild conditions, a decarboxylation reaction occurs, and a double salt of an oxide of calcium oxide (CaO) and magnesium oxide (MgO) called "lightly fired dolomite" is obtained. If water is added to lightly burned dolomite and digested, hydroxide dolomite, which is a double salt of a hydroxide of calcium hydroxide (Ca (OH) ₂ ) and magnesium hydroxide (Mg (OH) ₂ ), is obtained. . Hydroxide dolomite may contain other components such as calcium carbonate, calcium oxide, magnesium carbonate, magnesium oxide, silicon dioxide, aluminum oxide, and ferric oxide as long as the effects of the present invention are not impaired.

The mass ratio [Ca (OH) ₂ / Mg (OH) ₂ mass ratio] of calcium hydroxide to magnesium hydroxide contained in the hydroxide dolomite is preferably 10/90 to 90/10, and 20/80 to 85 /. 15 is more preferred, and 40/60 to 80/20 is even more preferred. When the mass ratio is within the above range, the properties of both the calcium component and the magnesium component can be fully utilized.

As the above-mentioned hydroxide dolomite, hydroxide dolomite specified in JIS R9001 and No. 1 are preferable.
Further, lightly fired dolomite can be used as a raw material of the hydroxide dolomite. As the lightly fired dolomite, the lightly fired dolomite specified in JIS R9001 and No. 1 is suitable. Lightly burned dolomite reacts with water contained in an object to be treated and raw materials, is hydrated by digestion, and changes to hydroxide dolomite. Therefore, even if the step of preparing the hydroxide dolomite is omitted and the lightly burned dolomite is used as it is, the effect of the hydroxide dolomite is exhibited.

BET specific surface area of the alkaline powder is preferably 0.5~60m ² / g, and more preferably 10 to 60 m ² / g. When the amount is 0.5 to 60 m ² / g, the area of contact (adsorption) with the odorous gas can be maintained. The BET specific surface area in this specification means a specific surface area calculated by a one-point method from a nitrogen adsorption amount by a BET method using nitrogen adsorption.

The average particle diameter (median diameter (d50)) of the alkaline powder is preferably from 2 to 40 μm, more preferably from 2 to 10 μm. When the thickness is 2 to 40 μm, a contact (adsorption) area with an odor gas can be maintained. The median diameter (d50) in the present specification means the particle diameter (d50) at which the integrated value of the number of particles in the particle size distribution obtained by the laser diffraction scattering method becomes 50%.
Also, in consideration of coating properties and drop-out preventing properties, the maximum particle size of the alkaline powder obtained by sieving is preferably 150 μm or less.

(Inorganic silica powder)
The inorganic silica-based powder is an inorganic powder containing silica as a chemical component.
Examples of the inorganic silica-based powders include powders containing silica as a chemical component, such as activated clay, acid clay, diatomaceous earth, silica gel, shale (in particular, fired expansive shale), perlite, allophane, zeolite, and the like. In particular, the inorganic silica-based powder is preferably an inorganic silica-based acidic powder in which the pH of an aqueous solution or dispersion is 6 or less. Inorganic silica-based acidic powder is a powder having a pH of 6 or less (preferably 4 or less, more preferably 3 or less) when 10 g of this is added to 100 ml of pure water and stirred or dissolved or dispersed for about 3 minutes. Say. By using the inorganic silica-based acidic powder, a synergistic effect with the alkaline powder can be easily obtained.
Preferred examples of the inorganic silica-based acidic powder include activated clay and diatomaceous earth.

BET specific surface area of the inorganic silica-based powder is preferably 70~200m ² / g, more preferably 90~190m ² / g. When it is 70 to ²⁰⁰ m ² / g, a contact (adsorption) area with an odorous gas can be maintained.

The average particle diameter (median diameter (d50)) of the inorganic silica-based powder is preferably from 10 to 200 μm, more preferably from 20 to 190 μm. When the thickness is 10 to 200 μm, a contact (adsorption) area with an odor gas can be maintained.
In consideration of coatability and drop-out prevention, the maximum particle size of the inorganic silica-based powder obtained by sieving is preferably 150 μm or less.

Pore volume of inorganic silica-based powder is preferably 0.1~0.5cm ³ / g, and more preferably 0.2~0.4cm ³ / g. When it is 0.1 to 0.5 cm ³ / g, the area of contact (adsorption) with the odorous gas can be maintained. The pore volume can be measured by a gas adsorption type pore distribution measuring instrument “NOVA-4200” (manufactured by Seishin Enterprise Co., Ltd.).

  The cation exchange capacity (CEC) of the inorganic silica-based powder is preferably from 10 to 200 meq / 100 g, more preferably from 10 to 100 meq / 100 g, and preferably from 10 to 50 meq / 100 g. More preferred. The cation exchange capacity can be measured by the method described in Examples described later.

  Here, the activated clay is a clay mineral derivative obtained by subjecting so-called bentonite or acidic clay, which is mainly composed of montmorillonite, to an acid treatment with sulfuric acid or the like to increase its activity. For example, the bentonite or the acid clay is dried at room temperature to form a powder, which is heated with an appropriate amount of an acid such as sulfuric acid at a temperature of 90 ° C. or more under normal pressure or pressure. Then, what was separated by filtration, washed, and dried at 120 to 200 ° C. is used. The activated clay has been subjected to an acid treatment such as sulfuric acid in order to enhance the surface activity, and exhibits strong acidity due to the orientation of the molecules on the surface.

  Examples of the commercially available activated clay include, for example, activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, and G-168 (all manufactured by Japan Activated Clay Co., Ltd.); Earth (NVZ, NF2, NFX, V2), Mizuka Ace (all manufactured by Mizusawa Chemical Industry Co., Ltd.); and the like.

  In addition, diatomaceous earth is a natural substance mainly composed of diatom-deposited silica, and Wakkanai diatomaceous earth produced in the Wakkanai region of Hokkaido is preferred from the viewpoint of good pore volume, but of course, those produced outside the Wakkanai region are also used. it can.

  The content of the alkaline powder with respect to the total of the alkaline powder and the inorganic silica-based powder is preferably from 10 to 90% by mass, and more preferably from 25 to 75% by mass. When the content is 10 to 90% by mass, odor removal and antibacterial action can be favorably exhibited.

  The total amount of the alkaline powder and the inorganic silica-based powder in the antibacterial deodorant is preferably 90% by mass or more, and more preferably 95% by mass. When the content is 90% by mass, the removal of odor and the antibacterial action can be favorably exhibited.

In addition to the alkaline powder and the inorganic silica-based powder, a powder such as activated carbon may be contained.
The average particle diameter (median diameter (d50)) of such a powder is preferably from 10 to 200 μm, more preferably from 20 to 190 μm.

  One embodiment of the antibacterial deodorant of the present invention can be prepared by mixing the above-mentioned alkaline powder and the above-mentioned inorganic silica-based powder. The mixing method is not particularly limited.

  The antibacterial deodorant thus manufactured can be applied to uses such as the treatment of carcasses of pets and the treatment of carcasses of livestock. It is also a preferred embodiment to use the method in the antibacterial deodorizing method described below (particularly, the antibacterial deodorizing method for corpses).

  Thermoplastic resin fibers can be used as the fibers constituting the nonwoven fabric sheet according to the present embodiment. Examples of the thermoplastic resin constituting the thermoplastic resin fiber include polyolefin, polyester, polyamide, and acryl. Examples of the polyolefin include polyethylene (PE), polypropylene (PP), polybutylene (PB), and a copolymer mainly composed of these. Examples of the polyester include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and copolymers mainly composed of these. Examples of the polyamide include nylon 6, nylon 6,6 and the like. Examples of the acrylic include polyacrylonitrile (PAN).

  As the fibers constituting the nonwoven fabric sheet, other fibers can be used in addition to or instead of the thermoplastic resin fibers. Examples of other fibers include natural fibers (eg, pulp, wool, cotton, etc.), regenerated fibers (eg, rayon, acetate, etc.), and inorganic fibers (eg, glass fibers, carbon fibers, etc.).

The basis weight of the nonwoven fabric sheet according to the present embodiment is preferably 10 to 150 g / m ² , more preferably 30 to 100 g / m ² , and more preferably 40 to 60 g / m ² from the viewpoint of handleability and flexibility. m ² is more preferable.

For the production of the non-woven fabric sheet, ordinary non-woven fabric production technology can be adopted.
Specific examples include a spunlace method, a spunbond method, a wet method, an air laid method, a chemical bond method, and a melt blow method. It can also be manufactured by combining these manufacturing methods. A preferred manufacturing technique is a spunlace method in which the fibers are loosely bound by entanglement of the fibers with a stream of water.

In order to form the antibacterial deodorant-containing resin region on the nonwoven fabric sheet, a coating liquid containing the above-described antibacterial deodorant and a water-insoluble binder may be applied to the nonwoven fabric sheet and dried.
The method of applying the composition to the nonwoven fabric sheet is not particularly limited, but a coating method using a comma coater, a knife coater, a gravure coater, or the like, or a method using flexographic printing or the like is preferable. In addition, a method using (flat) screen printing, rotary (screen) printing, inkjet, spraying, T-die, or the like can also be used. Especially, it is preferable to use a gravure coating method. In the case of the gravure coating method, the antibacterial deodorizing sheet has better flexibility as compared with other coating methods, especially the dipping method, the knife method, and the roll method.

In the case of the gravure coating method, the gravure depth (plate depth) is preferably 50 to 210 μm, and specifically, a gravure roll having a gravure depth of 60 μm, 90 μm, 150 μm, and 200 μm is preferable.
As the coating amount of the coating liquid is preferably 10 to 100 g / ^{m 2,} and more preferably 10 to 80 g / ^{m 2.} At this time, the coating amount of the antimicrobial deodorant in the coating liquid is preferably from 3 to 90, and more preferably 5 to 70 g / ^{m 2.}

After applying the coating liquid to the nonwoven fabric sheet by any of the above methods, known drying is performed.
As the method, a method of drying with hot air or infrared rays, a method of drying by contacting with a heat source, or the like may be used, and depending on the temperature and humidity, natural drying may be used. However, in the case of natural drying, the antibacterial deodorant absorbs moisture and carbon dioxide in the air, and the effect may be reduced. Therefore, it is preferable to dry at about 80 to 150 ° C.

  The pH of the antibacterial deodorizing sheet of this embodiment is preferably 11.5 or more, and more preferably 12 or more. When the pH is 11.5 or more, a good antibacterial effect can be exhibited. The pH of the antibacterial deodorizing sheet can be measured by the method described in the examples.

[2] Antibacterial deodorizing method One aspect of the antibacterial deodorizing method of the present invention is a method of arranging the antibacterial deodorizing sheet according to the present embodiment in the vicinity of an odor source and in the vicinity thereof. Here, the odor includes, for example, a putrefaction gas containing an ammonia gas and a hydrogen sulfide gas, particularly a putrefaction gas generated from a dead body left unattended. In some cases, acetic acid gas may be contained.

The odor generation source includes, for example, a place where ammonia gas and hydrogen sulfide gas coexist and are generated. The vicinity of the putrefaction gas generation source includes, for example, a place where ammonia gas and hydrogen sulfide gas, and in some cases, acetic acid gas coexist.
In addition, in addition to the ammonia gas, the hydrogen sulfide gas, and the acetic acid gas, methyl mercaptan, trimethylamine, skatole, and the like may be present in the odor generation source and the vicinity thereof.
In addition, the above-mentioned odor generation source usually has a putrefactive substance.Therefore, at least one of bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Salmonella is present, and in some cases, Infectious bacteria may be present.

In particular, in the case of a corpse (for mortuary processing), for example, the antibacterial deodorizing sheet according to the present embodiment may be used as a source of odors such as the neck and lower abdomen, and at a portion with lymph nodes (particularly the cervix, axilla, groin, And abdomen) and where there is a hole through which bodily fluids leak out. In addition, the vicinity thereof may be arranged at a location where a lymph node is present, around a hole through which body fluid leaks, inside a coffin, at its lid, or the like. In these odor sources, odor (dead odor) due to putrefaction and its concentration are high, and bacteria are easily propagated. If the antibacterial deodorizing sheet according to the present embodiment is arranged in such a place, the corpse can be stored in a sanitary manner. In addition, body fluids (mainly water) may leak from the corpse with long-term storage, but it is also significant that the components contained in the antibacterial deodorant may also exert a water absorbing action. I can say.
Therefore, as a preferable embodiment of the antibacterial deodorizing sheet of the present invention, an antibacterial deodorizing sheet for mortuary can be mentioned.

  Next, the present invention will be specifically described with reference to experimental examples and examples, but the present invention is not limited to these.

[Experimental example of antibacterial deodorant]
(Ammonia gas adsorption test with inorganic silica powder)
As the inorganic silica-based powder, activated clay powder (SA-1 manufactured by Nippon Activated Clay Co., Ltd.), zeolite powder (Zikulite SGW manufactured by Zikulite Co., Ltd.), diatomaceous earth powder (diatomaceous earth manufactured by Wakkanai Green Factory Co., Ltd.) 0.7 mm) was weighed, and an ammonia gas adsorption test was performed. Table 1-1 and Table 1-2 below show the properties, physical properties, and chemical components of the inorganic silica-based powder.

In this example, d50 (particle diameter at which the integrated value of the number of particles in the particle size distribution is 50%) and d90 (particle diameter at which the integrated value of the number of particles in the particle size distribution is 90%) are a laser diffraction type particle size distribution measuring apparatus. It was measured by "SALD-2300" (manufactured by Shimadzu Corporation).
The specific surface area was calculated from the amount of adsorbed nitrogen by the one-point method by the BET method using a gas adsorption type pore distribution analyzer “NOVA-4200” (manufactured by Seishin Enterprise Co., Ltd.).
The pore volume was also calculated using a gas adsorption type pore distribution measuring device “NOVA-4200” (manufactured by Seishin Enterprise Co., Ltd.).
The pH was measured by using a pH meter after collecting 10 g of each sample, adding it to 100 ml of pure water, and thoroughly stirring the mixture using a glass rod for 3 minutes.
In addition, the chemical components were measured by a method specified in “A method for analyzing lime” of JIS R9011.

  The method for measuring the cation exchange capacity will be described below. In the following description, “M” represents “mol / liter”, “L” represents “liter”, and “mL” represents “milliliter”.

(1) Preparation of reagent i) 1M ammonium acetate solution 77.08 g of ammonium acetate was dissolved in 1 L of pure water, and then the pH was adjusted to 7 with a 2M aqueous ammonia solution and 2M acetic acid to adjust the pH to 1M. A liquid was prepared.
ii) Ethanol (0.8 m ³ / m ³ )
100 mL of pure water was added to 800 mL of ethanol, and the pH was adjusted to 7 with ammonia water using BTB test paper.
iii) sodium chloride solution (10% by mass)
Pure water was added to 100 g of sodium chloride to make 1 L.
(2) Operation-exchange-
A sample (0.1 g) was dispensed into a centrifuge tube. Thereto, 40 mL of a 1M ammonium acetate solution was added. The mixture was allowed to stand in a thermostat at 25 ° C. with appropriate shaking. Thereafter, the mixture was centrifuged at 5000 rpm, and the supernatant was discarded.
(3) Operation-washing-
Next, 40 mL of ethanol was added thereto, shaken, centrifuged at 5000 rpm, and the supernatant was discarded. This washing operation was repeated four times, and then dried at room temperature.
(4) Operation-leaching-
After drying, 40 mL of a sodium chloride solution was added, and the mixture was allowed to stand for 24 hours while being appropriately shaken in a thermostat at 25 ° C. Thereafter, the mixture was centrifuged at 5000 rpm, the supernatant was collected, and the volume was adjusted to 50 mL with pure water.
(5) Measurement A constant volume (20 ml) was accurately measured from the permeated sodium chloride solution having a constant volume of 50 mL, and NH ₄ ⁺ was quantified by a Bremner distillation apparatus to obtain a cation exchange capacity.

  In addition, the adsorption test was performed in a Tedlar bag (5 liters) filled with an inorganic silica-based powder so that ammonia gas was filled at 50 ppm, and after 5, 10, 30, and 60 minutes, respectively. The concentration of ammonia gas was measured using a gas detector tube (manufactured by Gastech Co., Ltd.). Table 2 below shows the results of the ammonia gas adsorption test. The results when no acidic powder is used (blank) are also shown.

  From Table 2, all the inorganic silica-based powders had good ammonia gas adsorption characteristics.

(Experimental examples 1 to 3)
-Experimental example 1
As alkaline powder, 1 g of slaked lime (industrial special name slaked lime manufactured by Yoshizawa Lime Industry Co., Ltd.) shown in Table 3 below was used, and the inorganic silica-based powder was subjected to the above-mentioned "ammonia gas adsorption test using inorganic silica-based powder". 1 g of the used activated clay powder was used and mixed to prepare an antibacterial deodorant.

-Experimental example 2
1 g of the slaked lime used in Example 1 was used as the alkaline powder, and 1 g of the zeolite powder used in the above "Ammonia gas adsorption test using the inorganic silica powder" was used as the inorganic silica-based powder. Produced.

-Experimental example 3
1 g of the slaked lime used in Example 1 was used as the alkaline powder, and 1 g of the diatomaceous earth used in the above "Ammonia gas adsorption test using the inorganic silica powder" was used as the inorganic silica powder, and these were mixed to prepare an antibacterial deodorant. did.

・ Ammonia gas adsorption test:
Using 1 g of each of the antibacterial deodorants prepared in Experimental Examples 1 to 3, an ammonia gas adsorption test was performed in the same manner as the "ammonia gas adsorption test using inorganic silica-based powder". The results are shown in Table 4 below.

  From Table 4, all antibacterial deodorants had good ammonia gas adsorption characteristics, and the antibacterial deodorants of Experimental Examples 1 and 3 were particularly excellent.

・ Hydrogen sulfide gas adsorption test:
Except that the ammonia gas was hydrogen sulfide gas and the hydrogen sulfide gas concentration was 20 ppm, in the same manner as in the above “Ammonia gas adsorption test”, 1 g of each of the antibacterial deodorants prepared in Examples 1 to 3 was used. A hydrogen gas adsorption test was performed. The results are shown in Table 5 below.

  From Table 5, all antibacterial deodorants had good hydrogen sulfide gas adsorption characteristics.

(Experimental Examples 4 to 7 and Comparative Experimental Examples 1 and 2)
An antibacterial deodorant was prepared in the same manner as in Experimental Example 1 except that the ratio of slaked lime to activated clay was as shown in Table 6 below. Using 1 g of each prepared antibacterial deodorant, an ammonia gas adsorption test and a hydrogen sulfide gas adsorption test were performed in the same manner as in Experimental Example 1. The results are shown in Tables 6 and 7 below.

・ Antibacterial test:
According to the test method referred to "JIS Z 2801: 2012 Antibacterial processed product / Antibacterial test method / Antibacterial effect", the antibacterial deodorants (20 g) of Experimental example 1, Experimental examples 4 to 6, Comparative experimental examples 1 and 2 were used. The antibacterial effect of the stored pack (test product) against various bacteria at normal temperature (25 ° C.) was examined. Specifically, the test was performed as follows.

(1) Cleaning of the test article Both surfaces of the test article were irradiated with a pulsed xenon lamp (Comet, BHX-200) for 20 seconds to clean them.
(2) Test conditions i) Operating temperature and humidity: 25 ± 1 ° C, 90% RH or more
ii) Action time: Immediately (unprocessed test product only), 24 hours

(3) Test bacteria and preparation of test bacteria solution i) Test bacteria a) Escherichia coli NBRC3972 (Escherichia coli)
b) Staphylococcus aureus NBRC12732 (Staphylococcus aureus)
ii) Preparation of test bacterial solution The cryopreserved bacterial strain was cultured on a normal agar medium (Nissui Pharmaceutical) at 35 ± 1 ° C. for 24 hours. This culture was transferred to a new ordinary agar medium and cultured at 35 ± 1 ° C. for 19 hours. Scraped growth and settlements, and adjusted to about 10 ⁵ cells / mL in 1/500 concentration of nutrient broth medium (Eiken Chemical), which was used as a test bacterial solution.

(4) Test method The test method referred to "JIS Z 2801: 2012 Antibacterial processed product, Antibacterial test method, Antibacterial effect". Details are shown below.
i) Inoculation and culture of test bacterial solution The test product was placed in a petri dish, and 0.4 mL of the test bacterial solution was dropped at nine places on the entire surface of the test product. After the dripped test bacterial solution has been infiltrated, the surface of the bacterial solution inoculated is turned upside down and the working temperature / humidity condition (25 ° C. ± 1 ° C., 90% RH) in order to increase the contact efficiency between the contents in the pack and the bacterial solution. ) For a predetermined time.

ii) Measurement of bacterial count After the action for a predetermined time, the test product was collected in a sterilization bag for stomacher containing 100 mL of SCDLP bouillon medium (Eiken Chemical) in advance, and the test bacteria were washed out of the test product. The washed out solution was used as a sample solution for measuring the number of bacteria. For the sample solution, a dilution line was prepared using a phosphate buffered saline solution, 1 mL each of the sample solution stock solution and the diluent solution was transferred to a Petri dish, mixed with about 20 mL of a standard agar medium (Nissui Pharmaceutical), and then solidified. The cells were cultured at ± 1 ° C. for 48 hours. The number of growth colonies after the culture was counted, and the number of test bacteria per test product (lower limit of quantification: 100 / test product) was determined. Further, the antibacterial activity value of each antibacterial processed product was determined from the obtained number of test bacteria using the unprocessed test product as a control.
The test results for Staphylococcus aureus are shown in Tables 8 and 9 below, and the test results for Escherichia coli are shown in Tables 10 and 11 below.

The antibacterial activity value (R) was determined from the following equation.
_{Wherein: R = (U t -U o} ) - (A t -U o) = U t -A t
R: Antibacterial activity value (numerical values are rounded down to the second decimal place and displayed with one decimal place)
U _t: unprocessed specimen inoculation numerical viable count pairs immediately U _o: unprocessed specimen viable count of pairs after each action time of the numerical A _t: living bacteria after each exposure time of antibacterial products Logarithmic value of number

In both test bacteria, in each of the experimental examples, the value was less than the lower limit of quantification after 24 hours of action. The antibacterial activity value of Escherichia coli was 4.4 in all Examples, and that of S. aureus was 3.5.
The “antibacterial effect” in the test standard “JIS Z 2801” used as a reference indicates that the antibacterial activity value for a 24-hour action against Escherichia coli and Staphylococcus aureus as test bacteria is 2.0 or more. It can be seen that the antibacterial deodorant according to the example exhibited an excellent antibacterial effect.

[Example of antibacterial deodorant sheet]
(Examples 1 to 6 and Comparative Examples 1 and 2)
The following antibacterial deodorant and the following binder resin were mixed in the composition shown in Table 12 below to prepare an antibacterial deodorant-containing resin composition (coating liquid). This was applied to one surface of a nonwoven fabric sheet by gravure coating, and dried at 100 to 105 ° C for 90 to 100 seconds to prepare an antibacterial deodorant sheet having an antibacterial deodorant-containing resin region.
The following shows the antibacterial deodorant, binder resin, and gravure application conditions.

(1) Antibacterial deodorant: A mixture of activated clay powder (SA-1 manufactured by Japan Activated clay Co., Ltd.) and slaked lime for industrial use (manufactured by Yoshizawa Lime Industry Co., Ltd.) (mass ratio 1: 1).
(2) Binder resin:
・ Polyvinyl acetate; vinylol SH (manufactured by Showa Denko KK)
・ Polyurethane; urethane adhesive GOF-V medium (manufactured by Osaka Printing Ink Manufacturing Co., Ltd.)
・ Polyvinylpyrrolidone; Creasus (Daiichi Kogyo Seiyaku Co., Ltd.)
(3) Nonwoven fabric sheet: Examples 1 to 5 used spunlace nonwoven fabric A, and Example 6 and Comparative Examples 1 and 2 used spunlace nonwoven fabric B. Details of the nonwoven fabrics A and B are as follows.
・ Spunlace nonwoven fabric A; NA92050 (manufactured by Sanwa Paper Co., Ltd.)
・ Spunlace nonwoven fabric B; Escot CO60P / A01 (manufactured by Unitika Ltd.)

  With respect to the antibacterial deodorant sheets of Examples 1 to 6, the sheets were cut into 4 cm × 4 cm squares, poured into 50 ml of pure water, and the pH of the solution after stirring was measured with a pH meter (antibacterial). PH measurement of deodorant sheet). The results are shown in Table 12 below.

In each example, a gas adsorption test was performed on each of ammonia and hydrogen sulfide, similarly to the experimental example, using an antibacterial deodorant sheet having a size of 1 g of the antibacterial deodorant. A gas adsorption test for acetic acid (acetic acid gas concentration in a Tedlar bag (5 liter): 100 ppm) was also performed in the same manner. The results are shown in Table 12 below.
In addition, the case where the gas concentration after 60 minutes elapsed was less than 5 ppm was evaluated as ○, the case where the gas concentration was 5 ppm or more and less than 10 ppm was evaluated as Δ, and the case where the gas concentration exceeded 10 ppm was evaluated as X.
After the preparation of the antibacterial deodorant sheet, the antibacterial deodorant-containing resin layer was rubbed with a finger to check whether or not the powder could fall off. The results are shown in Table 13 below. In addition, when the powder did not adhere to the finger and did not fall off, it was evaluated as ○, and when the powder adhered to the finger or dropped off, it was evaluated as ×.

  According to Tables 12 and 13, the antibacterial deodorant sheets according to Examples 1 to 6 exhibited an antibacterial deodorizing effect well, and the antibacterial deodorant did not fall off.

・ Antibacterial test:
According to the test method with reference to "JIS Z 2801: 2012 antibacterial processed product / antibacterial test method / antibacterial effect", the unprocessed nonwoven fabric sheet and the antibacterial deodorant sheet of Example 4 (both may be referred to as "test products") ) Was tested for antibacterial effect against various bacteria at normal temperature (25 ° C.). Specifically, the test was performed as follows.
The unprocessed nonwoven fabric sheet (also referred to as “unprocessed test product”) is a nonwoven fabric before applying the antibacterial deodorant-containing resin composition of Example 4.

(1) Cleaning of the test article Both surfaces of the test article were irradiated with a pulsed xenon lamp (Comet, BHX-200) for 20 seconds to clean them.
(2) Test conditions i) Operating temperature and humidity: 25 ± 1 ° C, 90% RH or more
ii) Action time: Immediately (unprocessed test product only), 24 hours

(3) Test bacteria and preparation of test bacteria solution i) Test bacteria a) Escherichia coli NBRC3972 (Escherichia coli)
b) Staphylococcus aureus NBRC12732 (Staphylococcus aureus)
ii) Preparation of test bacterial solution The cryopreserved bacterial strain was cultured on a normal agar medium (Nissui Pharmaceutical) at 35 ± 1 ° C. for 24 hours. This culture was transferred to a new normal agar medium and cultured at 35 ± 1 ° C. for 17 hours. Scraped growth and settlements, and adjusted to about 10 ⁶ cells / mL in 1/500 concentration of nutrient broth medium (Eiken Chemical), which was used as a test bacterial solution.

(4) Test method The test method referred to "JIS Z 2801: 2012 Antibacterial processed product, Antibacterial test method, Antibacterial effect". Details are shown below.
i) Inoculation and culture of test bacterial solution A 50 mm square coating film (polyethylene film) was placed on a sterilized petri dish (90 mm in diameter), and the test article was placed thereon. 0.2 ml of the test germ solution was dropped at nine locations on the entire surface of the test product. A 50 mm square coating film was placed on the dropped test bacterial solution, and the test bacterial solution was adhered so as to spread over the entire coating film. The test product after inoculation of the bacterial solution was allowed to act for 24 hours under the operating temperature and humidity conditions. In addition, three test articles were subjected to the test (n3).

ii) Measurement of bacterial count After the action for a predetermined time, the test sample was collected in a sterilization bag for stomacher containing 10 mL of SCDLP bouillon medium (Eiken Chemical) in advance, and the test sample was washed out from the test sample. The washed out solution was used as a sample solution.
For the sample solution, a dilution line was prepared using a phosphate buffered saline solution, 1 mL each of the sample solution stock solution and the diluent solution was transferred to a Petri dish, mixed with about 20 mL of a standard agar medium (Nissui Pharmaceutical), and then solidified. The cells were cultured at ± 1 ° C. for 48 hours. The number of growth colonies after the culture was counted, and the number of test bacteria per test product (lower limit of quantification: 10 / test product) was determined. Further, the antibacterial activity value of each antibacterial processed product was determined from the obtained number of test bacteria, using the unprocessed test product as a control.
The test results for Escherichia coli are shown in Table 14 below, and the test results for Staphylococcus aureus are shown in Table 15 below.

The antibacterial activity value (R) was determined from the following equation.
_{Wherein: R = (U t -U o} ) - (A t -U o) = U t -A t
R: Antibacterial activity value (numerical values are rounded down to the second decimal place and displayed with one decimal place)
U _t: unprocessed specimen inoculation average of number of living bacteria logarithm U just after _o: No processing specimens of the mean A t logarithm of the number of viable bacteria after each exposure _time: antibacterial products (performed Average value of logarithmic value of viable cell count after each action time in Example 4)

The “antibacterial effect” in the reference test standard “JIS Z2801” is such that an antibacterial activity value against Escherichia coli or Staphylococcus aureus as a test bacterium in a 24-hour action is 2.0 or more. As is clear from Tables 14 and 15, in Examples, the antibacterial activity value for both test bacteria exceeded 2.0, and an excellent antibacterial effect was recognized.
Further, the antibacterial effect was improved when the antibacterial deodorizing sheet was used rather than in the state of the powder comprising the antibacterial deodorant. This is presumably because the use of the antibacterial deodorizing sheet caused a gap between the powders and increased the effective surface area of the powders.

Claims (8)

A nonwoven fabric sheet, an antibacterial deodorant, and an antibacterial deodorant sheet including a water-insoluble binder resin,
On at least one surface side of the nonwoven fabric sheet, has an antibacterial deodorant-containing resin region including the antibacterial deodorant and the water-insoluble binder resin,
The water-insoluble binder resin is a vinyl acetate resin,
The antimicrobial deodorant contains an alkaline powder having an aqueous solution or dispersion having a pH of 12 or more, and an inorganic silica-based powder,
An antibacterial deodorizing sheet wherein the pH of the antibacterial deodorizing sheet is 11.5 or more. The antibacterial deodorizing sheet according to claim 1, wherein a mixing ratio of the water-insoluble binder resin to 100 parts by mass of the antibacterial deodorant is 30 to 600 parts by mass. The antibacterial deodorizing sheet according to claim 1 or 2 , wherein the content of the alkaline powder is 10 to 90% by mass based on the total of the alkaline powder and the inorganic silica-based powder. The antibacterial deodorizing sheet according to any one of claims 1 to 3 , wherein the alkaline powder is slaked lime powder and / or dolomite-based powder. The antibacterial deodorizing sheet according to any one of claims 1 to 4 , wherein the inorganic silica-based powder is an inorganic silica-based acidic powder whose aqueous solution or dispersion has a pH of 6 or less. An antibacterial deodorizing method comprising disposing the antibacterial deodorizing sheet according to any one of claims 1 to 5 at and / or in the vicinity of an odor source. The antibacterial deodorizing method according to claim 6 , wherein the odor is a putrefaction gas, and includes an ammonia gas and a hydrogen sulfide gas. The antibacterial deodorizing method according to claim 7 , further comprising acetic acid gas as the putrefaction gas.