Antimicrobial composition, antimicrobial coating agent, and antimicrobial fiber sheet

Abstract

To provide an antimicrobial composition having excellent antimicrobial performance for inhibiting proliferation of bacteria in head sweat, exhibiting a high effect of eliminating head sweat odor, and especially excellent in durability of the effect.SOLUTION: An antimicrobial composition containing, based on nonvolatile matter, 70-99.5 wt.% of a photocatalyst semiconductor, 0.05-5 wt.% of an antimicrobial agent, and 1-25 wt.% of a binder, wherein the photocatalyst semiconductor includes at least one selected from the group consisting of peroxotitanic acid-modified anatase-type titanium oxide sol, rutile-type titanium oxide, and tungsten oxide, the antimicrobial agent includes at least one selected from the group consisting of diiodomethyl-p-tolylsulfone, silver ion, and copper ion, and the binder includes at least one selected from the group consisting of peroxotitanic acid, an acrylic binder, and a silica binder.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antibacterial composition, and more particularly to an antibacterial composition that can be used as an antibacterial coating agent when preparing an antibacterial fiber sheet. [Background technology]

[0002] The head, in particular, has many sebaceous glands, so head sweat contains a lot of sebum. Therefore, if head sweat adheres to headwear such as wigs, hats, and helmets and bacteria grow on it, a foul odor will be generated. The foul odor generated when bacteria grow on head sweat will be referred to as "head sweat odor" hereinafter. Furthermore, if headwear on which bacteria have grown comes into contact with the scalp, skin inflammation may occur. Therefore, there are fiber sheets that are placed between the headwear and the scalp when putting it on to absorb head sweat generated after putting it on. This is a device that aims to prevent scalp inflammation and head sweat from adhering to the headwear by periodically replacing such fiber sheets. The odorous components that contribute to head sweat odor are thought to be as follows:

[0003] 1. Sebum-related compounds: (1) Free fatty acids: Fatty acids produced by bacteria breaking down sebum (2) Squalene oxide: Oxidized squalene, one of the main components of sebum

[0004] 2. Sweat-related compounds: (1) Lactones: formed by the metabolism of certain fatty acids (2) Amines: Products formed by microbial decomposition of amino acids in sweat

[0005] 3. Microbial metabolic products: (1) Isovaleric acid: a metabolic product of leucine produced by certain bacteria (2) 3-Methyl-2-hexenoic acid: a metabolite of normal skin bacteria such as Malassezia

[0006] 4. Effects of hormonal changes: (1) Androgen: Sebum secretion influenced by male hormones

[0007] Patent Document 1 describes a hair pad that absorbs and adsorbs secretions such as sweat and sebum generated on the head into absorbent fibers, and also applies a chemical containing a hair growth agent to the head to promote hair growth and disinfection, protecting the hair and scalp while also preserving head accessories. Nonwoven fabric fibers can be used as the base absorbent fiber, and it is said that using hexachlorophene, Irgasan, chlorhexidine, etc. as the disinfectant base is effective.

[0008] Patent Document 2 describes a deodorizing, antibacterial, and moisture-absorbing device for headgear that is stored in the internal space of headgear to remove moisture from the internal space, and that includes at least one of a fabric containing bamboo fiber, a bamboo charcoal block, and a nonwoven fabric pad containing bamboo charcoal fiber.The deodorizing, antibacterial, and moisture-absorbing device for headgear in Patent Document 2 contains multiple bamboo charcoal blocks stored in a bamboo cloth bag containing bamboo fiber, so that sweat and odorous components evaporated from the scalp can be adsorbed by each bamboo charcoal block and the outer fabric. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 08-291415 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-7927 Summary of the Invention [Problem to be solved by the invention]

[0010] The antibacterial materials used in conventional antibacterial fiber sheets have insufficient antibacterial properties to inhibit bacterial growth in head sweat, making it difficult to prevent and eliminate head sweat odor. In general, deodorization refers to preventing the generation of bad odors, and deodorization refers to reducing the level of bad odors that occur to the point where they are no longer perceived as bad odors. In this specification, the term "deodorization" refers to both the general deodorization and deodorization described above.

[0011] The present invention solves the above problems, and an object of the present invention is to provide an antibacterial composition that has excellent antibacterial properties, a strong deodorizing effect, and excellent durability of the deodorizing effect. [Means for solving the problem]

[0012] The present invention provides the following aspects. [1] An antibacterial composition comprising, based on the nonvolatile content, 70 to 99.5 wt %, preferably 80 to 98 wt %, more preferably 85 to 95 wt % of a photocatalytic semiconductor, 0.05 to 5 wt %, preferably 0.1 to 4 wt %, more preferably 0.3 to 2 wt % of an antibacterial agent, and 1 to 25 wt %, preferably 3 to 20 wt %, more preferably 5 to 15 wt % of a binder, the photocatalytic semiconductor comprises at least one selected from the group consisting of peroxotitanic acid-modified anatase-type titanium oxide sol, rutile-type titanium oxide, and tungsten oxide; the antibacterial agent comprises at least one selected from the group consisting of diiodomethyl-p-trimethylsulfone, silver ions, and copper ions; The antibacterial composition, wherein the binder comprises at least one selected from the group consisting of peroxotitanic acid, an acrylic binder, and a silica binder.

[0013] [2] The antimicrobial composition of embodiment 1, further comprising up to 100 ppm, based on nonvolatile content, of an antioxidant.

[0014] [3] The antibacterial composition of Aspect 2, wherein the antioxidant comprises at least one selected from the group consisting of platinum colloid and vitamin C.

[0015] [4] An antibacterial coating agent comprising the antibacterial composition according to any one of embodiments 1 to 3 and an aqueous solvent.

[0016] [5] An antibacterial fiber sheet comprising the antibacterial composition of any one of Aspects 1 to 3 and a fiber sheet.

[0017] [6] 0.5~5g / m 2 , preferably 1 to 4 g / m 2 , more preferably 2 to 3 g / m 2 Photocatalytic semiconductor, 0.001~0.3g / m 2 , preferably 0.005 to 0.1 g / m 2 , more preferably 0.01 to 0.03 g / m 2 of antibacterial agent, and 0.01 to 3 g / m 2 , preferably 0.05 to 1 g / m 2 , more preferably 0.1 to 0.4 g / m 2 The antibacterial fiber sheet of embodiment 5, comprising a binder.

[0018] [7] The antibacterial fiber sheet according to aspect 5 or 6, wherein the fiber sheet is a nonwoven fabric.

[0019] [8] An antibacterial sweat-absorbing pad for the head, comprising the antibacterial fiber sheet according to any one of embodiments 5 to 7.

[0020] [9] A sweat-absorbing antibacterial pad for wigs, comprising the sweat-absorbing antibacterial pad of embodiment 8.

[0021]

[10] A method for deodorizing head sweat odor, comprising absorbing head sweat with the antibacterial fiber sheet according to any one of aspects 5 to 7. [Effects of the Invention]

[0022] According to the present invention, an antibacterial composition is provided that has excellent antibacterial properties that inhibit bacterial growth, a strong deodorizing effect, and excellent durability of the deodorizing effect. Use of the antibacterial composition of the present invention also provides an antibacterial coating agent and an antibacterial fiber sheet that have the excellent antibacterial properties, strong deodorizing effect, and excellent durability of the deodorizing effect. The antibacterial fiber sheet of the present invention has the excellent antibacterial properties, strong deodorizing effect, and excellent durability of the deodorizing effect, and is particularly durable to washing. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, one embodiment of the present invention will be described in detail, but the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values are specified for a specific parameter, any upper and lower limit values can be combined to form a suitable numerical range.

[0024] The antibacterial composition of the present invention contains an active ingredient that is an antibacterial material such as a photocatalytic semiconductor and an antibacterial agent. The antibacterial composition of the present invention may be solid or liquid. In one embodiment, the antibacterial composition of the present invention is solid.

[0025] <Photocatalytic semiconductor> The antibacterial composition of the present invention contains a photocatalytic semiconductor. The photocatalytic semiconductor can decompose organic matter through oxidation-reduction reaction. The photocatalytic semiconductor has high antibacterial and antiviral properties. The photocatalytic semiconductor used is one that can be dispersed or dissolved in a solvent. This makes it easy to uniformly bond the photocatalytic semiconductor to the substrate, and also improves the storage stability of the antibacterial composition.

[0026] As the photocatalytic semiconductor, at least one selected from TiO2, ZnO, SrTiO3, CdS, CdO, CaP, InP, In2O3, CaAs, BaTiO3, K2NbO3, Fe2O3, Ta2O5, WO3, SbO2, Bi2O3, NiO, Cu2O, SiC, SiO2, MoS2, MoS3, InPb, RuO2, CeO2, and composite oxides of titanium and silicon can be used.

[0027] The photocatalytic semiconductor can be one with a crystalline structure known as anatase or rutile. Among these photocatalytic semiconductors, titanium oxide having an anatase crystalline structure is preferably used because it has excellent photocatalytic activity. The photocatalytic semiconductor used is particularly preferably an aqueous sol of peroxotitanic acid-modified anatase titanium oxide. Reasons for the preferred use of the anatase type include its high transparency, its light absorption band extending to the visible light region, and its small particle size, which does not detract from the appearance.

[0028] The aqueous sol of peroxotitanic acid-modified anatase-type titanium dioxide can be obtained by heating an aqueous solution of peroxotitanic acid (described below) at 65°C or higher for 2 to 40 hours, preferably 4 to 15 hours, to convert part or all of the peroxotitanic acid into amorphous titanium dioxide, which then crystallizes into an anatase crystal precursor, followed by adding pure water to adjust the concentration of the titanium dioxide species. The concentration of the titanium dioxide species in the aqueous sol of peroxotitanic acid-modified anatase-type titanium dioxide is generally adjusted to 0.1 to 2.0% by weight, preferably 0.5 to 1.5% by weight.

[0029] The photocatalytic semiconductor is contained in the antibacterial composition in an amount of 70 to 99.5 wt % based on the non-volatile content. If the content of the photocatalytic semiconductor in the antibacterial composition based on the non-volatile content is less than 70 wt %, the deodorizing effect may be insufficient, while if it exceeds 99.5 wt %, when prepared as a coating agent, the liquid may lose transparency, or aggregation or precipitation may occur, resulting in reduced uniformity and stability. The content of the photocatalytic semiconductor in the antibacterial composition is preferably 80 to 98 wt %, more preferably 85 to 95 wt %.

[0030] When an aqueous sol of peroxotitanic acid-modified anatase-type titanium oxide is used, the content of titanium oxide species corresponds to the content of the photocatalytic semiconductor referred to here.

[0031] <Antibacterial agent> The antibacterial composition of the present invention contains an antibacterial agent. The antibacterial agent has the effect of inhibiting the growth of bacteria such as Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, ammonia-producing bacteria, Klebsiella pneumoniae, and black mold. Here, "antibacterial" is a concept that includes bactericidal, sterilizing, and bacteriostatic properties.

[0032] Examples of antibacterial agents include diiodomethyl-p-tolylsulfone, alum, quaternary ammonium salts, and hinokitiol. The antibacterial agent may be a metal-containing antibacterial agent. As the metal-containing antibacterial agent, a silver-based antibacterial agent containing silver or a copper-based antibacterial agent containing copper is preferred, as the antibacterial property of the present composition is more excellent. The silver may be in the form of, for example, metallic silver, silver ions, silver salts (including silver complexes), etc. Furthermore, the copper may be in the form of, for example, metallic copper, copper ions, copper oxide particles, copper-supported carriers in which these are supported on a carrier, etc. Specific examples of antibacterial agents containing metals include "Lunarsilver" (trade name) manufactured by Antibacterial Kaken Co., Ltd. and "Cufitec" (trade name) manufactured by NBC Meshtec Co., Ltd.

[0033] A preferred antibacterial agent is, for example, diiodomethyl-p-tolylsulfone, which has the advantages of excellent dissolution stability in the antibacterial composition of the present invention, being effective against mold, and having a significantly higher antibacterial effect.

[0034] The antibacterial agent is contained in the antibacterial composition in an amount of 0.05 to 5 wt % based on the nonvolatile content. If the content of the antibacterial agent in the antibacterial composition based on the nonvolatile content is less than 0.05 wt %, the antibacterial effect may be insufficient, while if it exceeds 5 wt %, the antibacterial effect may be too strong, potentially compromising safety for the human body and the environment. The content of the antibacterial agent in the antibacterial composition is preferably 0.1 to 4 wt %, more preferably 0.3 to 2 wt %.

[0035] <Solvent> The antibacterial composition of the present invention contains, as a solvent, 10 parts by weight or more of water to make a total of 100 parts by weight, and optionally an aqueous solvent obtained by mixing a small amount of a water-soluble alcohol such as ethanol, isopropanol, or methanol. The aqueous solvent may contain only water. On the other hand, when the antibacterial composition is prepared in the form of an aerosol spray, 20 to 60 parts by weight of ethanol may be added to the water.

[0036] By blending 10 parts by weight or more of water into this aqueous solvent, it is possible to suppress an increase in the particle size of the titanium oxide species used in the present invention, thereby improving the storage stability of the antibacterial composition. Furthermore, the higher the water content of the aqueous solvent, the longer it takes for the article coated with the antibacterial composition to dry, thereby increasing the safety of the manufacturing process. On the other hand, the higher the ethanol content of the aqueous solvent, the higher the wettability of the antibacterial composition to the coated article and the better the drying time.

[0037] The mixed solvent of the present invention can also be used in combination with other water-soluble organic solvents, such as other alcohols such as methanol and isopropanol, ketones such as acetone and methyl ethyl ketone, cellosolves such as butyl cellosolve and ethyl cellosolve, carbitols such as methyl carbitol, ethyl carbitol and butyl carbitol, and lactones such as γ-butyrolactone, as needed, within the scope of not interfering with the intended properties of the present invention.

[0038] <Base material> The antibacterial composition of the present invention can be used as an antibacterial coating agent for bonding an antibacterial material to a substrate. The substrate is typically a fiber sheet capable of absorbing sweat from the head. By bonding an antibacterial material to the fiber sheet, an antibacterial fiber sheet can be provided.

[0039] As the type of fiber sheet, any of knitted fabrics, woven fabrics, nonwoven fabrics, paper, etc. can be used. The fiber sheet may have either a single-layer structure or a multi-layer structure. A typical example is polypropylene (PP) spunbond (e.g., 1.9 dtex, basis weight 20 g / m 2 ), polyethylene terephthalate (PET) / rayon / PET spunlace (e.g., 1.7 dtex, basis weight 25 g / m 2 ), tissue containing pulp or rayon (e.g., basis weight 15 g / m2), etc. Nonwoven fabrics obtained by the through-air method or point-bonding method, and SMS (S: spunbond nonwoven fabric, M: meltblown nonwoven fabric or high-barrier material) three-layer nonwoven fabrics may also be used. Furthermore, substrates using fibers with a core-sheath or side-by-side structure such as PE (polyethylene) / PP or PE / PET may also be used. The fiber sheet may be biodegradable fabric, mask fabric, etc.

[0040] <Binder> The antibacterial composition of the present invention may optionally contain a binder. A binder is a material that binds the antibacterial material to a substrate. When the antibacterial composition contains a binder, the binding strength of the antibacterial material to the substrate is improved. As a result, the antibacterial fiber sheet of the present invention has improved washing durability, allowing the product to be used more hygienically.

[0041] Examples of binders that can be used include peroxotitanic acid, titanium peroxide, peroxotitanic acid, or amorphous titanium peroxide particles containing a metal oxide other than titanium, zeolite, and alkyl silicate. By using such a binder as a protective layer, it is possible to prevent the fiber sheet from being decomposed by the photocatalytic semiconductor.

[0042] Peroxotitanic acid can be obtained by the following method. First, titanium hydroxide, also known as orthotitanic acid, is obtained from a titanium compound (such as titanium chloride, e.g., titanium tetrachloride, or aqueous titanium sulfate solution) and a basic solution (such as ammonia or caustic soda). Next, by-products and impurities, such as ammonium ions and chloride ions, are removed by decantation using water, and the precipitated titanium hydroxide is separated. There are no particular restrictions on the concentration of the titanium compound, but the reaction is usually carried out in an aqueous solution obtained by diluting a commercially available aqueous solution with a concentration of 5 to 80% by weight to 0.3 to 10% by weight.

[0043] The pH for precipitating titanium hydroxide is preferably 1 to 3, more preferably about 2, to prevent impurities such as Fe from co-precipitating. The precipitation is preferably carried out at 5 to 40°C for 1 to 24 hours. The precipitated titanium hydroxide is sometimes called orthotitanic acid, and is in a gel state where it has polymerized due to OH-OH polymerization and hydrogen bonding, and cannot be used as is as a coating solution for a titanium oxide film.

[0044] Next, hydrogen peroxide solution is reacted with the separated titanium hydroxide to decompose and remove excess hydrogen peroxide, and pure water is added so that the concentration of titanium oxide species becomes 0.1 to 2.0 wt%, preferably 0.5 to 1.8 wt%, to obtain an aqueous solution of peroxotitanic acid. Here, the aqueous solution of peroxotitanic acid is prepared by adding a peroxotitanic acid complex (Ti2O5(OH) x (2-x)- Titanium oxide species, such as titanium dioxide (TiO(OH)2) and / or titanium dioxide hydrate (TiO(OH)2) dispersed in water, are believed to be dissolved, in a sol state, or in a dispersed form in water. Titanium oxide species, as used herein, include titanium dioxide having surface hydroxyl groups and are represented by the general formula Ti n O m (OH) x [wherein m and n are integers, and x has the same meaning as above].

[0045] When hydrogen peroxide is added to titanium hydroxide, some of the OH groups become peroxidized and dissolve as peroxotitanate ions, or form a kind of sol. The excess hydrogen peroxide decomposes into water and oxygen, making it possible to use the solution as a viscous liquid for forming titanium oxide films.

[0046] Examples of binders include peroxotitanic acid, hydrophilic acrylic binders, and silica binders.

[0047] The binder is contained in the antibacterial composition in an amount of 1 to 25% by weight based on the nonvolatile content. If the content of the antibacterial agent in the antibacterial composition based on the nonvolatile content is less than 1% by weight, the binding strength to the base may be insufficient. If it exceeds 25% by weight, the antibacterial fiber sheet after immersion processing may have a hard, uneven finish, or the physical properties and appearance of the antibacterial fiber sheet may be impaired. The content of the binder in the antibacterial composition is preferably 3 to 20% by weight, more preferably 5 to 15% by weight.

[0048] <Additives> In addition to the water-soluble polymer and antibacterial agent, the antibacterial composition may contain one or more optional additives, etc. Examples of such additional components include colorants, fragrances, deodorizers, antioxidants, UV protection agents, antistatic agents, pH adjusters, smoothing agents, dispersants, softeners, moisturizers, anti-inflammatory agents, and antihistamines.

[0049] The antibacterial composition can contain, for example, platinum colloid, vitamin C, fullerene, polyphenol, and other antioxidants, which act on the scalp to prevent the occurrence of blemishes and acne.

[0050] The antioxidant is contained in the antibacterial composition in an amount of up to 100 ppm based on the nonvolatile content. If the content of the antioxidant in the antibacterial composition based on the nonvolatile content exceeds 100 ppm, problems such as reduced uniformity and stability when prepared as a coating agent, impaired safety for the human body and the environment, and deterioration of the physical properties and appearance of the antibacterial fiber sheet may occur.

[0051] <Method for preparing antibacterial composition> The antibacterial composition can be prepared using a method that can uniformly mix the photocatalytic semiconductor, antibacterial agent, binder, and, if necessary, solvent and additives. A stirring device can be used to mix the components. Specific examples of stirring devices include a dissolver, static mixer, homogenizer, paint shaker, etc. The obtained antibacterial composition can be used as an antibacterial coating agent for bonding an antibacterial material to a substrate.

[0052] <Antibacterial coating agent and antibacterial fiber sheet> The antibacterial coating agent preferably contains an antibacterial composition and an aqueous solvent. The antibacterial composition contained in the antibacterial coating agent is preferably a non-volatile or solid component, and the aqueous solvent is a volatile component.

[0053] The type of antibacterial coating agent is not particularly limited, and may be a spray coating agent, a spread coating agent, a dip coating agent, etc. Depending on the type of antibacterial coating agent, the viscosity, solid content, and content of additives such as dispersants may be further adjusted.

[0054] An antibacterial material can be formed by bonding the antibacterial composition to a base material. Bonding of the antibacterial composition to a substrate can be achieved, for example, by applying or immersing the antibacterial coating agent on the substrate and drying it. Conventional coating devices can be used, such as contact-type slot coaters, roll coaters, and gravure coaters, or non-contact-type spray and spiral coaters. Among these, non-contact coaters are preferred because they can produce thin films and do not affect other processed areas, and spray coaters are particularly preferred. For example, it is preferable to heat the antibacterial coating agent to melt the water-soluble polymer, which is solid at room temperature, and then apply the antibacterial coating agent by spray coating. The heating temperature can be set appropriately, for example, at room temperature, about 80 to 250°C, or about 130 to 200°C.

[0055] The antibacterial composition may be bound to the base in any manner so long as the antibacterial composition remains on the base material without falling off under normal use conditions. In a preferred embodiment, the base comprises a fiber sheet, and the antibacterial material comprises an antibacterial fiber sheet. In the antibacterial fiber sheet, the antibacterial composition may be bound continuously or discontinuously to the surface (at least one side) of the fiber sheet or within the fiber sheet, or may be bound to part of the fiber sheet.

[0056] Antibacterial fiber sheet: 0.5 to 5 g / m 2 The content of photocatalytic semiconductor in the antibacterial fiber sheet is 0.5g / m 2 If the amount is less than 5g / m, the deodorizing effect may be insufficient. 2 If the content exceeds 100%, the degree of mixing with other antibacterial agents will decrease, making it difficult to apply the antibacterial fiber sheet uniformly. The content of the photocatalytic semiconductor in the antibacterial fiber sheet is preferably 1 to 4 g / m. 2 , more preferably 2 to 3 g / m 2 is.

[0057] Antibacterial fiber sheet: 0.001~0.3g / m 2 The antibacterial agent content of the antibacterial fiber sheet is 0.001g / m 2If it is less than 0.3g / m, the deodorizing effect may not last long enough. 2 If the content of the antibacterial agent in the antibacterial fiber sheet exceeds 0.005 to 0.1 g / m, the antibacterial activity may become too strong, which may compromise safety for the human body and the environment. 2 , more preferably 0.01 to 0.03 g / m 2 is.

[0058] Antibacterial fiber sheet: 0.01 to 3 g / m 2 The binder content of the antibacterial fiber sheet is 0.01g / m 2 If the amount is less than 3g / m, the deodorizing effect may not last long or the washing durability may be insufficient. 2 If the binder content exceeds 0.05 to 1 g / m, the antibacterial fiber sheet may have poor physical properties and appearance, such as a hard, uneven finish. 2 , more preferably 0.1 to 0.4 g / m 2 is.

[0059] The obtained antibacterial fiber sheet can be used as a sweat-absorbing antibacterial pad for head sweat absorption, which is placed between the headwear and the scalp when the headwear is worn. Specific examples of headwear include wigs, hats, helmets, kendo masks and helmets, etc. Wigs are often used under light exposure, and are therefore translucent, and their deodorizing function is enhanced by excitation of the photocatalytic semiconductor, making them a preferred headwear.

[0060] When the antibacterial fiber sheet is used as an antibacterial head sweat-absorbing pad, the shape and dimensions of the antibacterial fiber sheet may be further adjusted depending on the type of headgear, and additional absorbent materials such as fiber sheets, and materials for attachment and handling such as fasteners and belts may be added to the antibacterial fiber sheet.

[0061] The antibacterial fiber sheet and head sweat-absorbing antibacterial pad of the present invention have excellent deodorizing properties, and when they absorb head sweat, they do not produce head sweat odor for a long time even in a dark place.

[0062] In the antibacterial sweat-absorbing pad of the present invention, the antibacterial fiber sheet can be used as a surface or internal component. When used as a topsheet, it may be used as a part of the topsheet. Here, when used as a topsheet or a part thereof, the antibacterial fiber sheet preferably contains an antioxidant, which prevents the occurrence of blemishes, acne, etc. on the scalp. [Example]

[0063] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0064] Example 1 Manufacturing of antibacterial coating agents First, titanium hydroxide, also known as orthotitanic acid, is obtained from titanium tetrachloride and ammonia. Next, by-products and impurities such as ammonium ions and chloride ions are removed by decantation using water, and the precipitated titanium hydroxide is separated. Ammonium ions and chloride ions that remain after decantation are removed using ion exchange resin. Next, hydrogen peroxide is applied to the separated titanium hydroxide, and the mixture is stirred for 48 hours at 5°C to obtain an aqueous solution of peroxotitanic acid.

[0065] The aqueous solution of peroxotitanic acid was heated at 100°C for 9 hours to convert some or all of the peroxotitanic acid into amorphous titanium oxide, which was then converted to a precursor of anatase crystals, followed by anatase crystallization. Pure water was then added to adjust the concentration of the titanium oxide species, yielding an aqueous sol of peroxotitanic acid-modified anatase titanium oxide.

[0066] An antibacterial coating agent was obtained by adding diiodomethyl-p-tolylsulfone to a mixture of a peroxotitanic acid aqueous solution as a binder and a peroxotitanic acid-modified anatase-type titanium dioxide aqueous sol as a photocatalyst.

[0067] The obtained antibacterial coating agent contained 89.2% by weight of titanium oxide species, 10.0% peroxotitanic acid, and 0.8% diiodomethyl-p-tolylsulfone based on the nonvolatile content.

[0068] <Example 2> Manufacturing of antibacterial nonwoven sheets Nonwoven fabric sheet (Nisshinbo "Oikos AM2080" (product name), 100% cotton, basis weight 80g / m 2 ) was immersed in the photocatalytic solvent synthesized by the above method, squeezed with a mangle, and heat-treated at 160°C using a pin tenter method to obtain an antibacterial nonwoven sheet.

[0069] The antibacterial nonwoven fabric sheet contains 2.480g / m of titanium dioxide. 2 , diiodomethyl-p-tolylsulfone 0.0223g / m 2 , and peroxotitanic acid 0.2784 g / m 2 It included:

[0070] <Deodorizing test> 1. Original cloth As a pretreatment, the surface of the nonwoven fabric sheet obtained in Example 2 was irradiated with ultraviolet light (1 mW / cm 2 ) was irradiated for 3 hours. 2 The samples were placed in a sampling bag (a transparent film bag with a gas intake and exhaust port, "Smart Bag PA" manufactured by GL Sciences). Sampling bags were prepared for light conditions (irradiated with ultraviolet light) and dark conditions (not irradiated with ultraviolet light).

[0071] The sampling bag was filled with odorous gases, including ammonia (initial concentration 100 ppm) and acetaldehyde (initial concentration 14 ppm).

[0072] Immediately after, the samples were exposed to the specified ultraviolet light for 24 hours under light conditions. Blank tests were also conducted under both light and dark conditions. After 24 hours, the concentration of odorous components in the sampling bags was measured using a gas detector tube. The results are shown in Table 1.

[0073] 2. After washing The nonwoven fabric sheet obtained in Example 2 was washed according to the SEK Mark textile product washing method (standard washing method), revised on April 1, 2014. The washing procedure was repeated five times. Thereafter, the nonwoven fabric sheet washed according to the above method was subjected to a deodorizing test.

[0074] 3.Results The results of the deodorizing test are shown in Table 1.

[0075] [Table 1]

[0076] <Antibacterial test> In this example, an antibacterial test was carried out on Example 2 in accordance with JIS R 1702 (fine ceramics - antibacterial test method for photocatalytic antibacterial processed products under light irradiation - antibacterial effect).

[0077] [Table 2]

[0078] The outline of this antibacterial test is that a predetermined amount of a specific bacterial cell is inoculated onto a specimen of antibacterial fiber sheet carrying a photocatalytic solution, and then the specimen is cultured under specified conditions, and the number of viable bacteria is measured before and after the culture to evaluate the antibacterial properties. In this example, Staphylococcus aureus and Klebsiella pneumoniae were used and the test was carried out according to the glass contact method of JIS R 1702:2020. The light irradiation conditions were set to simulate a daytime indoor environment, with ultraviolet light at 0.01 mW / cm. 2 The antibacterial properties of each sample (photocatalytic solution) in this example were evaluated by calculating the antibacterial activity value and the effect of light irradiation specified in JIS R 1702 from the test results and comparing them as indices.

[0079] [Table 3]

[0080] In Table 3, S L ΔS is calculated using the following formula based on the Photocatalysis Industry Association's "Ultraviolet Light-Based Antibacterial (Antibacterial: Ultraviolet Light) Performance Evaluation Standards Explanation Document," June 13, 2021, pages 11-12. S L =log(M BL )-log(M L ) ΔS=(log(M BL )-log(M L ))-(log(M BD )-log(M D ))

[0081] Regarding the effect of light irradiation, it can be said that antibacterial activity was suppressed for a long period of time even in the dark.

Claims

1. An antibacterial composition comprising 70 to 99.5 wt % of a photocatalytic semiconductor, 0.05 to 5 wt % of an antibacterial agent, and 1 to 25 wt % of a binder, based on the nonvolatile content; the photocatalytic semiconductor comprises at least one selected from the group consisting of peroxotitanic acid-modified anatase-type titanium oxide sol, rutile-type titanium oxide, and tungsten oxide; the antibacterial agent comprises at least one selected from the group consisting of diiodomethyl-p-trimethylsulfone, silver ions, and copper ions; The antibacterial composition, wherein the binder comprises at least one selected from the group consisting of peroxotitanic acid, an acrylic binder, and a silica binder.

2. 10. The antimicrobial composition of claim 1, further comprising up to 100 ppm, on a nonvolatile basis, of an antioxidant.

3. 3. The antibacterial composition of claim 2, wherein the antioxidant comprises at least one selected from the group consisting of platinum colloid and vitamin C.

4. An antibacterial coating agent comprising the antibacterial composition according to any one of claims 1 to 3 and an aqueous solvent.

5. An antibacterial fiber sheet comprising the antibacterial composition according to any one of claims 1 to 3 and a fiber sheet.

6. 0.5 to 5 g / m ２ photocatalytic semiconductor, 0.001 to 0.3 g / m ２ of antibacterial agent and 0.01 to 3 g / m ２ The antibacterial fiber sheet according to claim 5, which contains a binder of the formula:

7. The antibacterial fiber sheet according to claim 5, wherein the fiber sheet is a nonwoven fabric.

8. A sweat-absorbing and antibacterial head pad comprising the antibacterial fiber sheet according to claim 5.

9. A sweat-absorbing and antibacterial pad for wigs, comprising the sweat-absorbing and antibacterial pad according to claim 8.

10. A method for deodorizing head sweat odor, comprising allowing the antibacterial fiber sheet according to claim 5 to absorb head sweat.

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