JP3369058B2 - Wet wiper - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet wiper for an object or a person, which is capable of imparting excellent antibacterial property and continuous antibacterial property to the surface of an object by wiping and drying the surface of the object. .

[0002]

2. Description of the Related Art The risk of nosocomial infection due to MRSA (methicillin-resistant Staphylococcus aureus) in the medical field is now becoming a social problem, and office equipment, office supplies and other unspecified people with antibacterial properties are given. It is desired to impart antibacterial properties so that articles that may come into contact with humans can be used safely and hygienically. Also, in general everyday life, interest in antibacterial articles has been increasing due to increasing cleanliness. Therefore, various methods for imparting antibacterial properties have been proposed. For example, Japanese Patent Laid-Open No. 2-25
Japanese Patent No. 5844 discloses the use of a resin composition containing a zeolite retaining antibacterial metal ions and a basic metal compound. The example shows an example in which a resin such as polypropylene or polyethylene is mixed with the above-mentioned antibacterial agent and injection molding is performed.

Japanese Unexamined Patent Publication (Kokai) No. 3-84066 discloses a resin composition containing an inorganic or organic composite particle carrying an antibacterial metal or an oxide thereof in a resin, and a molded article using the resin. The use is disclosed. JP-A 1-3
Japanese Patent No. 13531 discloses application of a synthetic resin molded body, in which powdery particles of water-soluble glass containing monovalent silver are mixed and supported, to a curtain for a bathroom, a bathtub or the like. Japanese Utility Model Publication No. 1-178876 discloses an antibacterial material made of a sheet obtained by fusing or adhering a thermoplastic resin sheet to a sheet made of a thermoplastic resin containing antibacterial zeolite,
An aseptic edible knife is disclosed that comprises the surface of the edible knife. These examples disclose a method of imparting a drug having antibacterial properties during the production of each article, and are related to desks, office equipment, office supplies, kitchen supplies, toiletries, household products, and walls that have been conventionally used. It does not propose a method of sterilizing any article such as a floor or imparting antibacterial property.

On the other hand, sterilization from the surface of any article,
The following methods have been proposed as methods for imparting antibacterial properties to the surface. For example, JP-A-63-63419
In the publication, tissue paper is wetted with water containing chlorhexidine glycolate, benzalkonium chloride, 2,4,4-trichloro-2-hydroxydiphenyl ether, etc., as a disinfectant at the time of use. After cleaning, a dry tissue paper for cleaning is disclosed which is used for the purpose of cleaning and deodorizing the body. Further, JP-A No. 64-25821 discloses a wetting method in which a paper or a non-woven fabric is impregnated with an aqueous solution of an inorganic acid salt or an organic acid salt of chitosan or quaternized chitosan as a natural and highly safe antibacterial agent. Tissue is disclosed. Japanese Unexamined Patent Publication No. 3-37017 discloses a wet tissue containing dextran sulfate or a salt thereof and an impregnating solution for the wet tissue, which has a bacteriostatic action for preventing the growth of bacteria, yeast and mold and a bactericidal action on the surface of an object. The wet tissue shown is disclosed.

In Japanese Patent Publication No. 25505/1993, 3-
A fibrous web formed of fibers in which a first antibacterial agent selected from the group consisting of (trimethoxysilyl) propyldidecylmethylammonium salt and 3- (trimethoxysilyl) propyloctadecyldimethylammonium salt is uniformly distributed. There is disclosed an antibacterial active wet wiper in which a liquid containing a second antibacterial agent selected from naturally occurring organic acids having antibacterial properties such as citric acid, sorbic acid and malic acid is impregnated with. Further, Japanese Patent Application Laid-Open No. 63-40558 discloses that
A toilet seat germicidal spray is disclosed in which a liquid in which a cationic surfactant or anionic surfactant is dissolved as a germicide in an alcohol such as methanol, ethanol, or isopropyl alcohol is contained in a spray container. They are,
At the same time as cleaning the surface of an arbitrary object, the surface of the object is sterilized by an antibacterial component contained in the base material or the impregnating liquid in the base material. However,
The methods using these agents have a problem that the antibacterial effect or the antibacterial activity immediately after wiping can be obtained, but the antibacterial effect cannot be continuously imparted after the wiping.

Further, Japanese Patent Laid-Open No. 63-275311 discloses impregnation with an impregnating solution in which a low molecular weight quaternary ammonium salt having a bactericidal action and an anionic high molecular weight quaternary ammonium salt are dissolved in hydrous alcohol. By cleaning it with a cleaning paper, it removes dirt and at the same time, it is a very thin polymer.
A method of forming a film of ammonium salt to obtain a long-lasting bactericidal effect is disclosed. However, since the film made of this high molecular quaternary ammonium salt is easily removed by contact with human fingers or the like, or by wiping with a wiping cloth or cloth containing water, it is necessary to obtain sufficient antibacterial sustainability. It didn't come.

[0007]

DISCLOSURE OF THE INVENTION In order to solve the above-mentioned problems, the present inventors have conducted extensive studies to achieve antibacterial persistence that does not easily fall off even by contact with an object or wiping with a wiping cloth. In a wet wiper obtained by impregnating a non-woven fabric or wet-resistant paper with an impregnating liquid containing one or more antibacterial components, at least one of the antibacterial components contained in the impregnating liquid is an antibacterial metal component and the antibacterial metal. By including antibacterial inorganic oxide fine particles composed of an inorganic oxide other than the components, it is possible to impart high antibacterial durability without easily falling off even with a wiping cloth containing water. The invention was completed. The purpose of the present invention is to
It is an object of the present invention to provide a wet wiper for an object or a person, which can impart excellent antibacterial properties and high antibacterial durability to the surface of an object.

[0008]

The first aspect of the present invention is a wet wiper obtained by impregnating a non-woven fabric or wet resistant paper with an impregnating liquid containing one or more kinds of antibacterial components, and the antibacterial components contained in the impregnating liquid. At least one of them contains antibacterial inorganic oxide fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component, and is contained in the impregnating liquid.
The solid content concentration of the antibacterial inorganic oxide fine particles is 0.003 to
It is a wet wiper characterized by being 0.05% by weight . A second aspect of the present invention is the wet wiper according to the first aspect of the present invention, wherein the antibacterial inorganic oxide fine particles contained in the impregnating liquid have an average particle diameter of 5 to 500 nm.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a liquid containing at least one antibacterial inorganic oxide fine particle composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component is used as a nonwoven fabric. Alternatively, it is a wet wiper which is contained in a paper substrate having wet resistance. The antibacterial component used in the present invention is composed of microparticles made of an antibacterial inorganic oxide, and is used in a colloidal solution in which the microparticles are dispersed in water. For example, JP-A-7-33616 or JP-A-6-36-16
The antibacterial component disclosed in Japanese Patent No. 80527 can be preferably used. The antibacterial inorganic oxide fine particles that can be preferably used in the present invention is a colloidal solution in which the fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed, The antibacterial metal component forms colloidal particles in the form of a mixture or compound with an inorganic oxide other than the antibacterial metal component, or is bound to the surface of the inorganic oxide colloidal particles other than the antibacterial metal component. There is. As the antibacterial metal component, a generally known antibacterial metal component can be used, for example, silver, copper, zinc, tin,
Examples include lead, bismuth, cadmium, chromium, mercury and the like. Particularly, one or more kinds of antibacterial metal components selected from silver, copper and zinc are preferable from the viewpoints of antibacterial action, discoloration and safety to human body.

Copper ion as an antibacterial component exhibits a blue color, while silver ion is originally colorless. However,
Silver ions become aggregates or oxides of metallic silver due to photochemical reaction or oxidation, and then turn brown or black. Particularly, in order to prevent the discoloration of the silver component due to the photochemical reaction of ultraviolet rays, it is preferable to use titanium, zirconium, cerium, zinc or the like in combination with the silver component. this is,
This is because the titanium, zirconium, cerium and zinc components act as an ultraviolet absorber and have the effect of preventing discoloration of the silver component. The amount of the antibacterial metal component in the antibacterial inorganic oxide fine particles that can be suitably used in the present invention is 0.1 to 25% by weight, preferably 0.1 to 15% by weight in terms of oxide based on the solid content. % Range. When the antibacterial metal component is less than 0.1% by weight, the antibacterial action is not sufficiently exhibited. Further, even if the amount of the antibacterial metal component is more than 25% by weight, there is no great difference in the antibacterial action as compared with the case of 25% by weight, and the silver component is not suitable because the discoloration tends to occur when the amount of this component is increased.

On the other hand, there is no antibacterial property suitable for use in the present invention.
Inorganic oxides other than antibacterial metal components in organic oxide fine particles
In addition, from the inorganic oxides that make up the known colloidal solution
The colloidal particles are
Oxide colloidal particles or complex oxide colloidal particles, or
Can be used by appropriately selecting these mixtures.
As a single oxide colloidal particle, SiO₂, Ti
O₂, ZrO₂, Fe₂O₃, Sb₂O_Five, WO₃Etc.
As the composite oxide colloidal particles,
Complex compounds with other inorganic oxide colloidal particles, for example
SiO₂・ Al₂O ₃, SiO₂・ B₂O₃, SiO₂・ P₂O
_Five, TiO₂・ CeO₂, TiO₂・ ZrO₂, SiO₂・ Z
rO₂, SnO₂・ Sb₂O_Five, SiO₂・ Al₂O₃・ Ti
O₂, SiO₂・ TiO₂・ CeO₂, TiO₂・ SiO₂・
ZrO₂, SiO₂・ Al₂O₃・ MgO, SiO₂・ Al₂
O₃・ CaO, SiO₂・ TiO₂・ Fe₂O₃Etc.
You can

The average particle size of the antibacterial inorganic oxide fine particles (colloidal particles) composed of the antibacterial metal component used in the present invention and the inorganic oxide other than the antibacterial metal component is 3
A range of up to 500 nm is desirable. The smaller this average particle diameter is, the more difficult it is to remove even by wiping with a wiping cloth containing water, and therefore, it is possible to impart the characteristics of excellent antibacterial durability. Therefore, the average particle diameter is in the range of 5 to 300 nm. More desirable. However, an average particle size of less than 3 nm is difficult to manufacture and causes a drastic increase in manufacturing cost, which is not desirable. On the other hand, when the average particle size exceeds 500 nm, even if it is 700 nm, it gives antibacterial properties to the surface of the article, and it also has a persistent antibacterial property, but if it is wiped with a wiping cloth containing water many times, the antibacterial properties are relatively fast. Therefore, the upper limit of the average particle size must be appropriately selected and determined according to the desired antibacterial sustainability. The wet wiper of the present invention is impregnated with a colloidal solution containing the above-mentioned antibacterial inorganic oxide fine particles, and by using the colloidal solution, desks, office equipment, office supplies, kitchen products, toiletry products, household products, walls, floors. The surface of the article is wiped and the impregnating liquid is transferred from the wet wiper to the surface of the wiped article, and the transferred impregnating solution is dried and the antibacterial inorganic oxide contained in the impregnating solution is dried. Since the fine particles are transferred to the wiped article and firmly bonded to the surface of the wiped article, not only the antibacterial property but also the high antibacterial durability is imparted to the surface of the article.

Therefore, the antimicrobial persistence on the surface of an article wiped with such a wet wiper is
The surface of the article and the antibacterial inorganic oxide fine particles having an average particle diameter of 500 nm or less, which are contained in the wet wiper and are determined by the binding force with the antibacterial inorganic oxide fine particles transferred to the surface of the article by wiping Since it can be firmly bonded, the antibacterial inorganic oxide fine particles can be wiped off even after being wiped and dried, and even after contact with human fingers or wiping with a cloth such as a cloth or a cloth containing water. It is difficult for the article to be transferred from the surface of the article to be transferred, and high antibacterial durability can be imparted. When the average particle size of the antibacterial inorganic oxide fine particles is larger than 500 nm, the binding force between the surface of the wiped article and the antibacterial inorganic oxide fine particles transferred to the article surface is sufficient as described above. Therefore, the antibacterial inorganic oxide fine particles tend to easily fall off when they are touched by human hands or wiped with a wiping cloth containing water. The smaller the average particle size of the antibacterial inorganic oxide fine particles, the stronger the bonded antibacterial inorganic oxide fine particles are bonded to the surface of the article when the target article is wiped and dried, and Although it is preferable because it has excellent sustainability, there is a limit to reducing the average particle size of the particles, and the limit value is 3 nm as described above.

The colloidal solution of the antibacterial inorganic oxide fine particles used in the present invention is an alkali metal, ammonium, or organic compound according to the method for producing a complex oxide colloidal solution described in, for example, JP-A-5-132309. A silicate of a base, an alkali-soluble inorganic compound, and an aqueous solution of an antibacterial metal component are simultaneously added to an alkaline aqueous solution having a pH of 10 or more to produce inorganic oxide colloidal particles containing the antibacterial metal component. Further, according to the production method described in JP-A-63-270620, an aqueous solution of titanic acid and an aqueous solution of an antibacterial metal component, which are obtained by adding hydrogen peroxide solution to a hydrous titanic acid gel or sol, Inorganic oxide colloidal particles may be produced by heat treatment in the presence of a silicon compound and / or a zirconium compound. Furthermore, in the method for producing an antibacterial agent comprising an antibacterial inorganic oxide colloidal solution described in JP-A-6-80527, in the colloidal solution in which the inorganic oxide colloidal particles having a negative charge are dispersed, After adding the aqueous solution, the colloidal solution may be heated at 60 ° C. or higher, preferably 100 to 200 ° C. As the aqueous solution of the antibacterial metal component used in the above-mentioned production method, for example, an ammine complex salt of zinc, silver, copper or the like obtained by dissolving a metal component selected from zinc oxide, silver oxide, copper oxide or the like in ammonia water is used. It is preferred to use an aqueous solution.

In the present invention, as the impregnating liquid containing the antibacterial component for the wet wiper, the colloidal solution in which the antibacterial inorganic oxide fine particles obtained as described above are dispersed is used, and a nonwoven fabric or a wet resistant material is used. A wet wiper containing an impregnating liquid having one or more kinds of antibacterial components is obtained by impregnating a base material having properties with an impregnating liquid, which is a dispersion medium for a colloidal solution in which antibacterial inorganic oxide fine particles are dispersed. Water can be replaced with an organic solvent by a known method to form a colloidal solution of antibacterial inorganic oxide fine particles using an organic solvent as a dispersion medium. These antibacterial inorganic oxide fine particles are dispersed. The colloidal solution can be prepared and used at a desired concentration by a known method using an ultrafiltration membrane. As an example of the colloidal solution of the antibacterial inorganic oxide fine particles that can be used in the present invention, a commercially available antibacterial agent (trade name: Atomie Ball, manufactured by Catalyst Kasei Kogyo Co., Ltd.) can be preferably used.

The solid content concentration of the antibacterial inorganic oxide fine particles contained in the impregnating liquid used is preferably in the range of 0.003% to 0.05% by weight. The amount of liquid that adheres to the wiped surface of the object by wiping when the object is wiped and cleaned using a wet wiper obtained by impregnating a non-woven fabric or a substrate having wet resistance with the impregnating liquid. Is slightly changed depending on the amount of the wetting liquid contained in the wet wiper, but the amount of the fine particles of the inorganic antibacterial agent transferred to the surface of the article tends to increase or decrease in proportion to the concentration of the fine particles contained in the wet wiper. However, if this solid content concentration is less than 0.003% by weight, it is too small, and antibacterial properties and antibacterial durability are obtained, but it is difficult to obtain sufficient effects.
Further, if the solid content concentration is increased to more than 0.05% by weight, the effect of antibacterial property and antibacterial durability is improved,
In terms of the ratio of addition of antibacterial agents, the effects of antibacterial properties and antibacterial sustainability level off, and it is not economically advantageous.

The impregnating solution for the wet wiper in the present invention is
At least one of the antibacterial components contained in the impregnating liquid is antibacterial inorganic oxide fine particles composed of the antibacterial metal component obtained as described above and an inorganic oxide other than the antibacterial metal component. Contains antibacterial ingredients. As the antibacterial component constituting the impregnating liquid, one kind or a mixture of plural kinds of the above-mentioned antibacterial inorganic oxide fine particles may be used, and in order to enhance the antibacterial effect and the immediate effect of antifungal effect, In addition to oxide fine particles, alcohols such as ethanol and isopropanol, paraoxybenzoic acid esters such as methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, and benzalkonium chloride. The impregnating liquid may be used by combining one or more kinds of organic acids such as a quaternary ammonium salt, citric acid, sorbic acid and malic acid, or other antibacterial agents, bactericides and preservatives.

In addition to the above-mentioned antibacterial inorganic oxide fine particles, when paraoxybenzoic acid esters or other antibacterial agents, bactericides, preservatives and the like are used together in the impregnating solution, they are impregnated with them. For the purpose of efficiently dissolving in
Glycols such as propylene glycol and butylene glycol may be added. Furthermore, for the purpose of enhancing the cleaning effect when wiping using a wet wiper, anionic surfactants such as carboxylates, sulfates, sulfonates, secondary amine salts, tertiary amine salts, Cationic surfactants such as quaternary ammonium salts, amino acid type amphoteric surfactants, betaine type amphoteric surfactants, sulfate ester salt type amphoteric surfactants, amphoteric surfactants such as sulfonic acid type amphoteric surfactants, polyethylene A surfactant such as a nonionic surfactant such as a glycol type nonionic surfactant or a polyhydric alcohol type nonionic surfactant may be added to the impregnating solution for use.

As the non-woven fabric or the substrate having wet resistance used for the wet wiper of the present invention, a known non-woven fabric, a wettability-provided fiber sheet or a non-woven fabric and a sheet obtained by laminating the above-mentioned sheet and compounding are used. But you can
Since it is desirable that the impregnating liquid can be sufficiently retained, it is preferable that hydrophilic fibers such as rayon fibers, pulp fibers, and cotton fibers are contained in all or part of the fibers. Examples of the non-woven fabric used in the present invention include non-woven fabric such as rayon non-woven fabric, cotton non-woven fabric, pulp non-woven fabric, or one or more types of hydrophilic fibers such as rayon fiber, cotton fiber, pulp fiber, and polyester fiber, A non-woven fabric in which one kind or a plurality of kinds of synthetic fibers such as polypropylene fiber, nylon fiber, and aramid fiber are combined can be preferably used. The basis weight of the nonwoven fabric or the substrate having wet resistance used for the wet wiper can be appropriately selected according to the application, but the basis weight measured by JIS L 1906 is in the range of 15 to 100 g / m ² , preferably 20 to 8
It is in the range of 0 g / m ² . If the basis weight is less than 15 g / m ² , the wet wiper is too thin to give a bad feeling in use and is likely to tear. On the other hand, if the basis weight exceeds 100 g / m ² and becomes large, the rigidity of the wet wiper becomes high and it becomes difficult to use.

The non-woven fabric used for the wet wiper or the substrate having wet resistance may be subjected to creping or the like for the purpose of improving flexibility, or may be used for increasing the surface strength and reducing the fallen fibers such as paper powder. In the known synthesis of, for example, an aqueous emulsion or latex of polyacrylic acid ester, polymethacrylic acid ester, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, nitrile-butadiene copolymer, polyester resin, polyurethane resin, etc. Polymer aqueous emulsion or latex is impregnated,
It may be applied using a spray method, a gravure coating method, or the like. The wet wiper of the present invention can be produced by impregnating a non-woven fabric or a substrate having wet resistance with the impregnating liquid containing the antibacterial inorganic oxide fine particles prepared as described above. The amount of the impregnating liquid can be arbitrarily adjusted according to the kind of the non-woven fabric to be impregnated or the substrate having wet resistance, the purpose of use, etc. 50 to 400% by weight based on the absolute dry basis weight measured by L 1906, preferably 10
It is in the range of 0% by weight to 300% by weight.

When the amount of the impregnating liquid is less than 50% by weight,
Moisture contained in the wet wiper is too small, resulting in unevenness when cleaning the surface of the target article, making it difficult to clean sufficiently evenly, and at the same time, the absolute amount of the antibacterial inorganic oxide fine particles contained in the wet wiper is small. Since the amount of the impregnating liquid transferred to the surface of the object is small, the amount of the antibacterial inorganic oxide fine particles transferred to the surface of the wiped article is small, which is sufficient for the surface of the wiped article. It is not suitable because it cannot impart antibacterial properties and antibacterial durability. On the contrary, if the impregnated amount exceeds 400% by weight, the amount of liquid contained in the wet wiper is too large, and when the target article is wiped, it is soaked in water and cannot be sufficiently wiped. Since the amount of impregnating liquid transferred to the surface of the cleaned article is too large, it takes too long to dry, which is not suitable. If the article that has been wiped in the undried state is used as it is, or if the surface of the article that has been wiped is wiped with a dry wiper before use, the antibacterial inorganic oxide fine particles on the surface of the article are removed. Or, it will fall off, and sufficient antibacterial properties and antibacterial durability cannot be imparted to the surface of the target article.

The wet wiper of the present invention is capable of imparting a highly durable antibacterial property to the surface of the target article by wiping the surface of the target article with this and then drying. The degree of antibacterial persistence that can be imparted to the surface by wiping the target article, the surface state and liquid absorption of the target article, the ease of transfer of the antibacterial inorganic oxide fine particles to the surface of the target article,
Since it changes depending on the method of drying after wiping and the like, it cannot be generally discussed, but for example, a smooth surface such as a stainless steel plate or a plastic plate is wiped with the wet wiper of the present invention once or twice, and then at room temperature. Once dried, the surface has antibacterial properties after being wiped once with a wiper containing water, preferably 3 times, and more preferably 5 times.

As described above, in the wet wiper of the present invention, at least one of the antibacterial components used is composed of an antibacterial inorganic component and an inorganic oxide other than the antibacterial metallic component. Contains oxide fine particles,
Using this wet wiper, wipe the surface of any article such as office desks, office equipment, office supplies, kitchen appliances, toiletries, household goods, walls, floors, etc., and then sterilize the surface by drying. At the same time, it is possible to impart excellent antibacterial durability to the surface of the target article.

[0024]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples,%
Unless otherwise specified, the term "%" means% by weight on an absolute dry basis.

Example 1 As a commercially available antibacterial agent, a wet wiper was prepared by using a colloidal solution (trade name: Atomie Ball-S, manufactured by Catalyst Kasei Kogyo Co., Ltd.) in which fine particles of antibacterial inorganic oxide having the following composition are dispersed. An impregnating solution was prepared. Composition of antibacterial inorganic oxide fine particles: average particle diameter: 10 μm, type of antibacterial metal component: silver, inorganic oxide other than antibacterial metal component: TiO2, solid of antibacterial metal component in antibacterial inorganic oxide fine particles % Per minute: 4.5% (as oxide), solid content concentration of antibacterial inorganic oxide fine particles contained in the colloidal solution: 1.5% It was prepared by mixing 1% of Atomie Ball-S) and 99% of ion-exchanged water. The impregnating liquid was impregnated into a composite non-woven fabric composed of wood pulp and polypropylene fibers (trade name: Texel A40Z, basis weight 40 g / m ² , manufactured by Shin Oji Paper Co., Ltd.) to prepare a wet wiper. The impregnation amount of the impregnation liquid was adjusted to be 200% based on the weight of the composite nonwoven fabric.

Example 2 An impregnating solution for wet wipers was treated with an antibacterial agent (Atomie Ball-
S) 0.5% and ion-exchanged water 99.5% were mixed and prepared. A wet wiper was produced in the same manner as in Example 1 except that this impregnating liquid was used. Example 3 An impregnating solution for wet wipers was treated with an antibacterial agent (Atomie Ball-
S) 2.0% and ion-exchanged water 98% were mixed and prepared. A wet wiper was produced in the same manner as in Example 1 except that this impregnating liquid was used.

Example 4 An impregnating solution for wet wipers was treated with an antibacterial agent (Atomie Ball-
S) 1%, ethanol 3%, propylene glycol 3
%, Methyl paraoxybenzoate 0.2%, ethyl paraoxybenzoate 0.1% and ion-exchanged water 92.7% were mixed and prepared. A wet wiper was produced in the same manner as in Example 1 except that this impregnating liquid was used.

Example 5 As a commercially available antibacterial agent, a wet wiper was prepared using a colloidal solution (trade name: Atomie Ball-L, manufactured by Catalyst Kasei Kogyo Co., Ltd.) in which fine particles of antibacterial inorganic oxide having the following composition are dispersed. An impregnating solution was prepared. Composition of antibacterial inorganic oxide fine particles: average particle size: 100 μm, type of antibacterial metal component: silver, inorganic oxide other than antibacterial metal component: TiO2, solid of antibacterial metal component in antibacterial inorganic oxide fine particles Concentration per minute: 4.5% (oxide conversion), solid content concentration of antibacterial inorganic oxide fine particles contained in the colloidal solution: 1.5% The impregnating solution for wet wipers is an antibacterial agent (Atomie Ball-
L) 1%, ethanol 3% and deionized water 96% were mixed and prepared. A wet wiper was produced in the same manner as in Example 1 except that this impregnating liquid was used.

Example 6 A colloidal solution prepared by dispersing antibacterial inorganic oxide fine particles in which the antibacterial metal component is silver and the inorganic oxide other than the antibacterial metal component is TiO ₂ is prepared by the method shown below. did. Preparation of colloidal solution Titanium sulfate was dissolved in pure water to prepare an aqueous solution containing 1.0% of TiO ₂ . 1 with stirring in this aqueous solution
Aqueous 5% ammonia water was gradually added to obtain a white slurry solution, which was filtered through a glass filter (G2), and the cake was thoroughly washed with water to obtain a hydrous titanic acid cake. 31.4g of this cake dried with 33% pure water
After adding 219.8 g of hydrogen peroxide solution having a concentration, the mixture was heated at 80 ° C. for 14 hours to obtain TiO _{2 at a} concentration of 1.0% and pH.
8.2, 3136 g of a yellowish brown transparent titanic acid solution was obtained.

Then, a 15% aqueous ammonia solution 2
0.64 g of silver oxide was dissolved in an aqueous ammonia solution prepared by diluting 1.3 g with 618.1 g of pure water to prepare an aqueous solution of silver ammine complex salt, and 15.4 g of ammonium zirconium carbonate was added to 169.9 g of pure water. What was melt | dissolved in was added and the mixed aqueous solution was obtained. This mixed aqueous solution was added to the titanic acid solution, and then 20% concentration of silica sol 3 was added.
After adding 8.7g, it heated at 150 degreeC for 36 hours. This solution was yellowish brown at the beginning, but after 36 hours, it became a light milky white colloidal solution composed of transparent antibacterial inorganic oxide fine particles. The composition of this colloidal solution is as follows. Solid content concentration: 12.0%, average particle diameter of antibacterial inorganic oxide fine particles: 5.5 nm, concentration of antibacterial metal component in antibacterial inorganic oxide fine particles per solid content: 1.3% (oxide Conversion),

The impregnating solution for wet wipers is 0.1% of the colloidal solution, 5.0% of ethanol, 0.5% of citric acid,
Methyl paraoxybenzoate 0.1% and ion-exchanged water 9
It was prepared by mixing with 4.3%. This impregnating liquid was applied to a non-woven fabric composed of cotton fibers (trade name: Oikos AP
2030, basis weight 30 g / m 2, manufactured by Nisshinbo Co., Ltd.
A wet wiper was made. The impregnation amount of the impregnation liquid was adjusted to be 250% based on the weight of the nonwoven fabric.

Example 7 A colloidal solution prepared by dispersing fine particles of antibacterial inorganic oxide composed of silver and zinc as the antibacterial metal components and SiO _{2 as} the inorganic oxide other than the antibacterial metal component was prepared by the following method. Prepared. A mixture of 20 g of a colloidal solution having a SiO ₂ concentration of 20% and 280 g of pure water was heated to 80 ° C. The pH of this mother liquor is 10.7, and 1500 g of a 1.5% sodium silicate aqueous solution as SiO ₂ and 0.5 as Al ₂ O ₃ are added to the mother liquor.
% Aqueous sodium ammine solution (1500 g) at the same time to obtain a silica / alumina composite oxide colloidal solution having a pH of 12.3, which is then concentrated by an ultrafiltration membrane to obtain a solid content concentration of 22.2%. Was prepared. On the other hand, 20 g of 0.08 g of silver oxide (reagent: special grade, manufactured by Wako Pure Chemical Industries, Ltd.)
Was suspended in pure water and then a 15% aqueous ammonia solution was added until the silver oxide was dissolved to prepare a silver ammine complex salt aqueous solution. In the same manner, 0.30 g of zinc oxide (reagent: special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved to prepare a zinc ammine complex salt aqueous solution.

The silver ammine complex salt aqueous solution and the zinc ammine complex salt aqueous solution are mixed, and water is added to adjust the concentration so that the total oxide concentration of silver oxide and zinc oxide is 0.5%. It was adjusted. This mixed ammine complex salt aqueous solution was added to the colloidal solution and stirred sufficiently, and then placed in an autoclave and heated at 150 ° C. for 6 hours. The colloidal solution containing the antibacterial inorganic oxide fine particles is one in which the antibacterial metal components are silver and zinc, and the antibacterial inorganic oxide fine particles are dispersed, and has the following composition. Solid content concentration: 5.0%, average particle diameter of antibacterial inorganic oxide fine particles: 8.2 nm, concentration of antibacterial metal component in antibacterial inorganic oxide fine particles per solid content: silver 1.5%, zinc 5.0% (both converted to oxides), the impregnating solution for wet wiper is 0.3% of the colloidal solution,
It was prepared by mixing 3.0% of ethanol and 96.7% of ion-exchanged water. A non-woven fabric composed of rayon fiber (trade name: Benliese JF601, weight 6
0 g / m2, manufactured by Asahi Kasei Kogyo Co., Ltd.) to obtain a wet wiper. The impregnation amount of impregnation liquid is 1 per weight of nonwoven fabric.
It was adjusted to be 50%.

Example 8 An impregnating solution for wet wipers was prepared by using 0.1% of the above-mentioned antibacterial inorganic oxide fine particles (Atomie Ball-S) and 99.
A wet wiper was produced in the same manner as in Example 1, except that the wet wiper was mixed with 9%. Example 9 A wet wiper impregnating solution was prepared by mixing 5.0% of the above-mentioned antibacterial inorganic oxide fine particles (Atomie Ball-S) and 95.
A wet wiper was produced in the same manner as in Example 1 except that the wet wiper was mixed with 0%.

Example 10 A zeolitic antibacterial agent was prepared as antibacterial inorganic oxide fine particles by the following method. Na-Y type zeolite was suspended in water to prepare 400 g of a slurry having a concentration of 5%. The slurry was heated to 70 ° C. and the concentration of AgN was 5%.
Ion exchange with silver was performed by adding 9.2 g of an O3 aqueous solution, heating to 90 ° C. and leaving it for 1 hour. This slurry is filtered through a glass filter (G2), the cake is thoroughly washed with warm water at 60 ° C., dried at 120 ° C., and further baked at 550 ° C. for 1 hour to prepare powdery antibacterial inorganic oxide fine particles. did. The antibacterial inorganic oxide fine particles contain a silver component of 1.5% in terms of oxide and have an average particle diameter of 700.
was nm. The antibacterial inorganic oxide fine particles were dispersed in ion-exchanged water so as to have a solid content concentration of 1.0% to prepare a dispersion liquid of the antibacterial agent. A wet wiper was prepared in the same manner as in Example 1 except that the impregnating solution for wet wiper was prepared by mixing 2.5% of the antibacterial agent dispersion, 5% of ethanol, and 92.5% of ion-exchanged water. did.

Example 11 A wet wiper impregnating solution was prepared by mixing 0.2% of the antibacterial agent dispersion prepared in Example 10, 5% ethanol and 94.8% ion-exchanged water. A wet wiper was prepared in the same manner as in Example 1.

Comparative Example 1 A wet wiper was prepared in the same manner as in Example 1 except that the impregnating solution for wet wiper was prepared by mixing 75% ethanol and 25% ion-exchanged water. Comparative Example 2 An impregnating liquid for a wet wiper was mixed with 5.0% ethanol, 5.0% propylene glycol, 0.2% methyl paraoxybenzoate, 0.1% ethyl paraoxybenzoate and 89.7% ion-exchanged water. Except that it was prepared by mixing
A wet wiper was produced in the same manner as in Example 1. Comparative Example 3 In the same manner as in Example 1 except that the impregnating solution for wet wiper was prepared by mixing 5.0% ethanol, 0.2% benzalkonium chloride and 94.8% ion-exchanged water. A wet wiper was made. Comparative Example 4 A wet wiper was produced in the same manner as in Example 1 except that only ion-exchanged water was used as the impregnating liquid for the wet wiper.

The performance of the wet wipers produced in the examples and comparative examples was subjected to the following tests to evaluate their quality. (1) Antibacterial and persistent antibacterial "Test strain" The test strain is a commonly used strain,
Klebsiella pneumoniae IF012732, a typical Gram-negative bacterium that exists in a general environment.
And Staphylococcus aureus (St.
aphylococcus aureus IF012732) was used. As a medium, a normal broth medium was used for the pre-culture, and a normal agar medium was used for the main culture. The composition of each medium is as shown below. Ordinary broth medium meat extract 5 g Heptone 10 g Sodium chloride 5 g Distilled water 1000 ml pH 7.0

Normal agar medium meat extract 5 g Heptone 10 g Sodium chloride 5 g Agar 15 g Distilled water 1000 ml pH 7.0 Phosphate buffer solution was prepared by dissolving 34 g of potassium dihydrogen phosphate in 500 ml of purified water (distilled water). After adjusting the pH to 7.2 by adding 175 ml of a% sodium hydroxide solution, purified water was added to make a total volume of 1000 ml to obtain a stock solution. The storage solution was stored at 5 ° C. or lower, and the storage limit was 2 months. At the time of use, this preservation solution was diluted 800 times and sterilized under high pressure steam.

"Antibacterial" Test Piece A wet wiper cut into a size of 20 mm × 20 mm was used as a test piece. Five test pieces were used for one evaluation. Antibacterial evaluation First, the test strain was tested at 37 ° C in normal broth medium for 2
After culturing for 4 hours, the culture solution was added to a preservative solution consisting of phosphate buffer solution that had been sterilized by high-pressure steam, and the bacterial concentration was 104 cells /
A test bacterial solution was prepared by diluting to give a volume of ml. 75 ml of this solution was put in an Erlenmeyer flask, and then 0.75 g of the test piece was put in an absolutely dry state. Then, this Erlenmeyer flask was put on a shaker and shaken under the conditions of 340 rpm, 28 ° C., and 60 minutes to sufficiently bring the bacteria in the bacterial solution into contact with the test piece. Next, 1 to 10 times to 100,000 times the bacterial solution
A 0-fold dilution series was prepared, and a plate was prepared by the pour method using 1 ml of each concentration of bacterial solution and 15 ml of normal agar medium.
After culturing for 48 hours in a 37 ° C. incubator, the colonies were counted, and the sterilization rate with respect to the number of bacteria before contact was calculated to evaluate the antibacterial property.

[Antibacterial Sustainability] Preparation of Sample Plate Size consisting of stainless plate (SUS316), ABS resin plate and soft PVC sheet is 100 mm × 100 mm.
The following three types of test plates were prepared. Next, paper kitchen towels (product name: Napier Kitchen Towel, Shin Oji Paper Co., Ltd.)
Impregnated with 75% ethanol, wipe the surface of each test plate with this towel, sterilize, clean and dry, then wipe with a paper kitchen towel soaked with ion-exchanged water and leave it indoors for 72 hours And dried. After that, each test plate was wiped back and forth four times using the wet wipers obtained in Examples and Comparative Examples, and dried at room temperature for 1 hour, and used as a sample plate for antibacterial persistence test (wiping frequency: 0 times). To do. The surface of each sample plate was wiped once with a paper kitchen towel impregnated with ion-exchanged water, and this was wiped 1 times in the antibacterial persistence test.
Sample plate for 2 times, and then similarly for the first time, 1 hour of drying time is followed by 2 hours for wiping, 2 times for wiping sample plate, and similarly for samples up to 7 times of wiping I prepared a board. There was a 1 hour drying time between each wipe.

Evaluation of Antimicrobial Sustainability First, the test strain was tested at 37 ° C. for 2 hours in normal broth medium.
After culturing for 4 hours, the culture solution was added to a preservative solution consisting of phosphate buffer solution that had been sterilized by high-pressure steam, and the bacterial concentration was 104 cells /
A test bacterial solution was prepared by diluting to give a volume of ml. 100 μl of this test bacterial solution was placed on the surface of each sample plate prepared as described above, left at 35 ° C. for 24 hours, and cultured. Next, the test bacterial solution after culturing on the surface of the sample plate is washed away with 10 ml of a preservation solution consisting of a phosphate buffer solution sterilized by high-pressure steam to obtain a bacterial solution. Next, a 10-fold dilution series from 10 times to 100,000 times the bacterial solution was prepared, and a plate was prepared by the pour method using 1 ml of the bacterial solution of each concentration and 15 ml of agar medium. Then, after culturing for 48 hours in a 37 ° C. incubator, colonies were counted, and the sterilization rate with respect to the number of bacteria before dropping on the sample surface was calculated to evaluate antibacterial persistence. At this time, when the number of bacteria in the bacterial solution was larger than the number of bacteria in the bacterial solution before dropping, it was indicated by a + symbol. It can be said that the higher the sterilization rate is, the stronger the antibacterial property and the antibacterial persistence are, but it can be said that the antibacterial property or the antibacterial persistence is provided when the sterilization rate is 65% or more. Furthermore, if the sterilization rate is 80% or more, it is very desirable because it has a very high antibacterial property or antibacterial durability.

The test results obtained are shown in Tables 1 and 2.

[0044]

[Table 1]

[0045]

[Table 2]

As can be seen from Tables 1 and 2, the wet wiper of the present invention has an excellent antibacterial property. When the object is wiped off with this wet wiper, the antibacterial property can be imparted to the surface of the object thereafter. The antibacterial property is maintained even after wiping the surface with water several times, and it has excellent antibacterial durability. That is, the particle diameter of the antibacterial inorganic oxide fine particles is 500 n
A wet wiper containing a liquid having a solid content concentration of the antibacterial inorganic oxide fine particles in the impregnating liquid of 0.003 wt% to 0.05 wt% under m was wiped seven times with a towel containing water. After that, it has antibacterial properties, and very high antibacterial persistence is obtained even after wiping at least 5 times (Examples 1 to 1).
7).

Even with a wet wiper containing a liquid having a solid content concentration of the antibacterial inorganic oxide fine particles lower than 0.003% by weight, the surface of the object wiped with the wiper has sufficient antibacterial property. However, the antibacterial property is maintained even after being wiped three times with a towel containing water, but in order to maintain the effect even after being wiped five times or more, it is necessary to increase the solid content concentration (Example 8). When the particle size is small and the solid content concentration exceeds 0.05% by weight and is large, it goes without saying that the antibacterial property and the antibacterial durability are extremely excellent, but the improvement of the effect has reached a ceiling, It is economically disadvantageous (Example 9). The particle size of the antibacterial inorganic oxide fine particles is 500n
Even when an antibacterial agent exceeding m is used, the antibacterial property is maintained by wiping with a towel containing water three times (Example 10).
~ 11). Even when the particle size is large and the solid content concentration of the antibacterial inorganic oxide fine particles in the impregnating liquid is lowered to less than 0.003% by weight, the antibacterial property that can withstand wiping about 3 times is imparted. (Example 11).

When ethanol is used as the antibacterial component, the bacteria can be sterilized by wiping and have antibacterial properties, but the antibacterial properties cannot be maintained when wiped with a towel containing water (Comparative Example 1). When paraoxybenzoic acid esters were included in the antibacterial component, antibacterial properties were obtained by wiping and wiping with a towel containing water showed some sterilization effect, but the effect was not sufficient and It was not the level that the sex was maintained (Comparative Examples 2-3). A wet wiper containing only ion-exchanged water has neither antibacterial property due to wiping nor antibacterial persistence (Comparative Example 4).

[0049]

INDUSTRIAL APPLICABILITY The present invention is used for desks, office equipment,
Office supplies, kitchen utensils, toiletries, household items,
The effect of sterilizing the surface of an arbitrary article such as a wall or floor and imparting an extremely excellent and lasting antibacterial property to the surface of the object is obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Tanaka 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu, Fukuoka Prefecture Catalytic Chemicals Co., Ltd. Wakamatsu factory (56) Reference JP-A-7-150075 (JP, A) JP-A-8-59404 (JP, A) JP-A-7-238183 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61L 2/16 A47L 13/17

Claims (2)

(57) [Claims] 1. A wet wiper obtained by impregnating a non-woven fabric or wet-resistant paper with an impregnating liquid containing one or more antibacterial components, wherein at least one of the antibacterial components contained in the impregnating liquid is
Containing antibacterial inorganic oxide fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component, the solid concentration of the antibacterial inorganic oxide fine particles contained in the impregnating solution
Wet wiper having a degree of 0.003 to 0.05% by weight . 2. The wet wiper according to claim 1, wherein the antibacterial inorganic oxide fine particles contained in the impregnating liquid have an average particle diameter of 5 to 500 nm.