JP2000016901A - Antimicrobial powder and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject powder, capable of keeping its antimicrobial effect for extended periods. SOLUTION: This antimicrobial powder comprises an antimicrobial agent composed of anionic, hydrophilic polymer and salt of quaternary ammonium showing antimicrobial effect, supported by a porous carrier. The useful porous carriers include silica, alumina, activated carbon, zeolite, diatomaceous earth, silica gel, perlite and silas balloons. The useful hydrophilic polymers include cellulose containing carboxylic group, starch containing carboxylic group, pectic acid, alginic acid, a derivative of one of the above, and (meth)acrylic acid. They may be used either individually or in combination as a copolymer. The useful salts of quaternary ammonium include the ones shown by the following formula: (R1 to R4 are each a saturated or unsaturated 1-30C aliphatic hydrocarbon or aralkyl, which may be the same or different, wherein at least one of R1 to R4 is a saturated or unsaturated 1-30C aliphatic hydrocarbon; and X is a halogen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial powder and a method for producing the same. More specifically, the present invention relates to an antibacterial powder which is stable in an aqueous solvent and is useful for maintaining antibacterial properties over a long period of time, and a method for producing the same.

[0002]

2. Description of the Related Art Salts of an anionic hydrophilic polymer and a quaternary ammonium salt are insoluble or hardly soluble in water by using a compound having antibacterial or antifungal properties as the quaternary ammonium salt. Soluble antibacterial or antifungal salts can be produced. Usually, an antibacterial agent or the like may be used by being applied (or coated) to a substrate or the like or mixed in advance with a substance to be imparted with antibacterial properties. By using an antimicrobial agent that is insoluble or hardly soluble in water, elution of antimicrobial components due to moisture (rainwater, moisture in the air, etc.) in the use environment can be prevented, and antimicrobial properties can be maintained for a long time. In addition to this, there is an advantage that it can be used for objects in which frequent use of water is inevitable (for example, bathrooms, pools, clothes, etc.).

Japanese Patent Application Laid-Open No. 9-291500 discloses a wet nonwoven fabric containing 0.3 to 0.5% by weight, based on a fibrous web, of a quaternary ammonium salt or an organic acid silver having an antibacterial and deodorant function. . It also describes that the quaternary ammonium salts or organic acid silver contained in the fiber web are used by being enclosed in zeolite. However, benzalkonium chloride, which is widely used as an antibacterial quaternary ammonium salt, is itself often hydrophilic, and elutes with moisture even when used in a zeolite or the like. Antibacterial properties are apt to be reduced by long-term use.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antibacterial powder and granule capable of maintaining an antibacterial property for a long time by supporting a water-insoluble or sparingly soluble antibacterial agent on a porous carrier. It is to provide a manufacturing method. Another object of the present invention is to provide an antibacterial powder useful for imparting antibacterial properties by mixing with a raw material and applying to a substrate while preventing elution by water, and a method for producing the same. It is in.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a porous carrier contains an anionic hydrophilic polymer and an antibacterial quaternary ammonium salt. It has been found that by carrying an antibacterial agent composed of a salt, the elution of the active ingredient can be suppressed even in an environment where moisture exists, and the antibacterial property can be maintained for a long period of time, and the present invention has been completed.

That is, the antibacterial powder of the present invention is obtained by supporting an antibacterial agent comprising a salt of an anionic hydrophilic polymer and a quaternary ammonium salt having antibacterial properties on a porous carrier. Can be As the porous carrier, inorganic porous particles such as silica, alumina, activated carbon, zeolite, diatomaceous earth, silica gel, perlite, and shirasu balloon can be used. Examples of the hydrophilic polymer include hydrophilic polysaccharides such as water-soluble homoglycans (eg, carboxyl group-containing cellulose, carboxyl group-containing starch, pectic acid, alginic acid and derivatives thereof), and hydrophilic resins such as carboxyl group-containing resins. (E.g., a homo- or copolymer of (meth) acrylic acid). Further, as the quaternary ammonium salt, those represented by the following formula (1) can be used.

[0007]

Embedded image (Wherein, R ^{1 to} R ⁴ are the same or different and each represents a saturated or unsaturated C _1-30 aliphatic hydrocarbon group, an aralkyl group, a mono- or dialkylphenoxy group, an alkyleneoxyalkyl group, a trialkylammoniumalkyl group. either shown, or two or three of R ¹ to R ⁴ may form a hetero ring together with the nitrogen atom. However, at least one saturated or unsaturated C _10-30 of R ¹ to R ⁴ (X represents a halogen atom.) The present invention also includes a method for producing an antibacterial powder in which the antibacterial agent is supported on a porous carrier.

[0008] In the present specification, the term "hydrophilic polymer" means a hydrophilic (water-soluble, water-affinity, water-dispersible) polymer or a water-insoluble water-absorbing polymer. In addition, “immobilization” means adding a hydrophilic (particularly water-soluble) quaternary ammonium salt to an aqueous solution of the hydrophilic polymer (particularly a water-soluble polymer) to form a salt, Insoluble or hardly soluble.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial powder of the present invention is obtained by supporting an antibacterial agent on a porous carrier, and the antibacterial agent comprises an anionic hydrophilic polymer and a fourth antibacterial agent. Consists of salts with quaternary ammonium salts. [Porous Carrier] The porous carrier used in the antibacterial powder of the present invention is not particularly limited as long as the activity of the antibacterial agent can be effectively exhibited, and various inorganic porous particles can be used. The inorganic porous particles can be composed of, for example, a porous material such as activated carbon, silica gel, alumina, zeolite, silica, silica-alumina, nickel-alumina, diatomaceous earth, perlite, and shirasu balloon, and have a large specific surface area as a carrier. Is preferred. When used for applications such as spraying, a porous material that is not in the form of fine powder is preferred from the viewpoint of non-scattering properties. These porous carriers can be used alone or in combination of two or more.

The specific surface area of the porous body can be selected from a wide range in which the antibacterial agent component can be effectively supported.
0.1 to 3000 m ² / g, preferably 1 to 3000 m
² / g (e.g., 1~1000m ² / g), more preferably 2~500m ² / g (e.g., 2 to 100 m ² /
g) range.

The average particle size of the porous material is in a wide range that does not impair the suitability for addition when mixed with a material imparting antibacterial properties, for example, 1
The range can be selected from a range of about 2000 μm, preferably about 5 to 1000 μm (for example, 10 to 500 μm). [Antibacterial agent] Anionic hydrophilic polymer The anionic hydrophilic polymer used in the present invention is not particularly limited as long as it can form a salt with a quaternary ammonium salt described below. Examples include anionic hydrophilic polysaccharides and anionic hydrophilic resins.

The anionic hydrophilic group includes -COO
_{H, -SO 3 H, -OSO 3} H, -H 2 PO 4 , or a derivative thereof, or the like their ammonium salts or alkali metal salts. Further, -NH ₂ , -CN,-
_{OH, -NHCONH 2, - (OCH} 2 CH 2) - other hydrophilic groups, such _{as, -NR 3 X, SO 3 NH} 2 CO -, -
N (SO ₃ H) - (where, R represents an alkyl group, X is a halogen atom) may have other hydrophilic groups such as. A preferred hydrophilic group is a carboxyl group (—COO
H).

The anionic hydrophilic polysaccharides include:
Any polysaccharide (homoglycan, heteroglycan, etc.) can be used as long as it has an anionic hydrophilic group in the molecule. Examples of the homoglycan include glucan (cellulose, starch, glycogen, caronine, laminaran,
Dextran), fructan (inulin, levan, etc.), mannan (elegans mannan, etc.), xylan (rice xylan, etc.), galacturonan (such as pectic acid), mannuronan (such as alginic acid), N-acetylglucosamine polymer (chitin) And their derivatives). Examples of the heteroglycan include diheteroglycan (guaran, konjac mannan, heparin, chondroitin sulfate, hyaluronic acid, etc.), triheteroglycan (plant mucilage such as meskit gum, gatch gum, gum, bacterial polysaccharide, etc.), tetratetraglycan Heteroglycans (eg, gums such as gum arabic, gums, bacterial polysaccharides, etc.), and derivatives thereof can be exemplified.

The hydrophilic polymer is preferably a water-soluble polysaccharide having a hydrophilic group as described above, more preferably a water-soluble homoglycan, and specifically, a carboxyl group-containing cellulose [carboxymethyl group-containing cellulose (For example, carboxymethylcellulose, carboxymethylmethylcellulose, carboxymethylethylcellulose, carboxymethylhydroxyethylcellulose,
Carboxymethyl hydroxypropyl cellulose, etc.)
Etc.], carboxyl group-containing starch (such as carboxymethyl starch), pectic acid and its derivatives (such as sodium pectate), and alginic acid and its derivatives (such as sodium alginate).

In forming the salt with the quaternary ammonium salt in the hydrophilic polysaccharide, when importance is placed on the fact that this salt is hardly soluble in water, the content of the carboxyl group is particularly limited. Can be selected according to the application. Further, when a salt that is hardly soluble in an organic solvent is desired, less than 1.5 (for example, 0.5
To about 1.3), preferably about 0.6 to 1.2, and more preferably about 0.6 to 1.0.

Among the above-mentioned carboxyl group-containing hydrophilic polymers, in particular, a hydrophilic polymer having a carboxymethyl group,
For example, when carboxymethyl group-containing cellulose (such as carboxymethyl cellulose (CMC) or a derivative thereof) or starch (such as carboxymethyl starch (CMS) or a derivative thereof) is used as an anionic hydrophilic polymer, the amount of carboxyl group introduced is reduced. It can be adjusted and a salt with a quaternary ammonium salt described later can be formed with high efficiency.

The CMC is represented by the following equation (2).

[0018]

Embedded image (In the formula, R ⁵ represents a hydrogen atom or a carboxymethyl group, and n is about 10 to 1500.) In the above formula (2), the amount of carboxymethyl group introduced into cellulose [degree of substitution of carboxymethyl group (D
S)] is represented by an average degree of substitution of a carboxyl group (carboxymethyl group) per one unit of an anhydrous glucose group. When a salt which is hardly soluble in water is desired, DS is 1.5 or more (for example, 1). When the salt is hardly soluble in both water and organic solvent, the DS is less than 1.5 (for example, 0.5 to 5).
1.3), preferably about 0.6 to 1.2, and more preferably about 0.6 to 1.0. In CMS, the amount of carboxymethyl groups introduced into starch can be selected from the same range as in CMC. If the DS value is less than 0.1, it is difficult to achieve practically sufficient antibacterial properties because the amount of the quaternary ammonium salt described below is small. Depending on the quaternary ammonium salt solubilized in the solvent or further introduced, it may be soluble in water.

The average polymerization degree n of CMC is 50-1.
500, preferably 100 to 1500 (for example, 400
１1200). When the average degree of polymerization is 10 or less,
It may show solubility in water and organic solvents.

Examples of the anionic hydrophilic resin include resins having a hydrophilic group as described above (homopolymers or copolymers of a polymerizable monomer having a hydrophilic group). Or a monomer containing a salt thereof (such as styrene sulfonic acid and its sodium salt);
Monomers containing a carboxyl group or a salt thereof (carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, monoalkyl maleate or salts thereof), and monomers containing an acid anhydride group (maleic anhydride) Acid or the like) or a copolymer. Further, the anionic hydrophilic resin can also be used as a copolymer of the above-described anionic group-containing monomer and another copolymerizable monomer.

Examples of the copolymerizable monomer include, for example,
Olefins or dienes (eg, ethylene, propylene, butadiene, etc.), dialkyl maleate, (meth) acrylic monomers (eg, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate , Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; vinyl cyanide such as glycidyl (meth) acrylate and (meth) acrylonitrile; (Eg, epoxy-containing monomers such as allyl alcohol, allyl isocyanate, allyl glycidyl ether, etc.), vinyl monomers (aromatic vinyl monomers such as vinyl isocyanate, styrene, vinyl pyrrolidone, vinyl imidazo) Such as heterocyclic vinylamines, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; hydrolyzable silyl group-containing monomers such as vinyl trisalkoxysilane; and halogen-containing vinyl monomers such as vinyl chloride and vinylidene chloride. And the like). These copolymerizable monomers can be used alone or in combination of two or more.

The preferred hydrophilic resin is a carboxyl group-containing hydrophilic resin and the like, and a homo- or copolymer of (meth) acrylic acid and a copolymer of (meth) acrylic acid and another polymerizable monomer are particularly preferable. .

In the anionic group-containing hydrophilic resin, the content of the anionic group-containing monomer can be selected within a range in which a salt insoluble in water and an organic solvent can be formed. ~ 100% by weight, preferably 5-50
%, More preferably 5 to 30% by weight (for example,
-20% by weight). These hydrophilic polymers can be used alone or in combination of two or more.

The hydrophilic polymer has a viscosity of a 1% by weight aqueous solution of 10 to 1500 mPa · s, preferably 50 to 1000 mPa · s.
mPa · s, more preferably about 50 to 500 mPa · s (for example, 100 to 300 mPa · s). Quaternary ammonium salt The antibacterial powder of the present invention comprises a salt of the anionic hydrophilic polymer and a quaternary ammonium salt having antibacterial properties. As the quaternary ammonium salt having antibacterial properties, a compound represented by the following formula (1) can be used.

[0025]

Embedded image (Wherein, R ^{1 to} R ⁴ are the same or different and each represents a saturated or unsaturated C _1-30 aliphatic hydrocarbon group, an aralkyl group, a mono- or dialkylphenoxy group, an alkyleneoxyalkyl group, a trialkylammoniumalkyl group. either shown, or two or three of R ¹ to R ⁴ may form a hetero ring together with the nitrogen atom. However, at least one saturated or unsaturated C _10-30 of R ¹ to R ⁴ In the formula (1), at least one of R _{1 to} R ₄ is an aliphatic hydrocarbon group.
One is a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and the other is a substituent such as an aralkyl group, a mono- or dialkylphenoxy group, an alkyleneoxyalkyl group, and a trialkylammoniumalkyl group. And two or three of R _{1 to} R ₄ may form a heterocyclic ring together with the nitrogen atom. The aliphatic hydrocarbon has a carbon number of 1 to 30, preferably 10 to 30 (for example, 1 to 30).
0-20).

The quaternary ammonium salt includes, for example,
Alkyltrimethylammonium halides (such as C _10-30 alkyl trimethyl ammonium chloride), alkenyl trimethylammonium halide (C _10-30 alkenyl trimethyl ammonium chloride, etc.), dialkyldimethylammonium halides (di -C _10-30 alkyl dimethyl ammonium chloride, etc.), Dialkenyl dimethyl ammonium halide (such as di-C _10-30 alkenyl dimethyl ammonium chloride), the following formula (3): [C ₆ H ₅ CH ₂ N (CH ₃ ) ₂ R ⁶ ] ⁺ X ⁻ (3) , R ⁶ represents an alkyl group and X represents a halogen atom)
_{Alkylbenzyldimethylammonium} halide [ _C10-30 alkylbenzyldimethylammonium chloride (benzalkonium chloride), 4- _{C1-9alkylphenyloxyethoxyethylbenzylbenzylammonium} chloride (eg benzethonium chloride, etc.)
And the like, and alkylpyridinium halides (N-C
Cyclic quaternary ammonium salts such as _10-30 alkylpyridinium bromide), alkylpiperidinium halide, alkylpyrrolium halide and alkylpyrrolidinium halide. In the halogen atom X,
Includes fluorine, chlorine, bromine and iodine.

In a preferred quaternary ammonium salt, R ¹ out of R ^{1 to} R ⁴ in the formula (1) is a linear or branched saturated or unsaturated C _10-30 aliphatic hydrocarbon group,
R ² is an aralkyl group. Further, R ³ and / or R ⁴
Is a linear or branched saturated or unsaturated C _1-9 aliphatic hydrocarbon group which may be the same or different. Among such compounds, benzalkonium chloride (for example, when R ¹ is C ₁₂ H
₂₅ , C ₁₄ H ₂₉ , when R ² and R ⁴ are a methyl group, and R ³ is a benzyl group).

The above quaternary ammonium salts having antibacterial properties can be used alone or in combination of two or more.

Particularly preferred salts for constituting the antibacterial powder of the present invention are at least one selected from carboxymethyl group-containing cellulose and carboxymethyl group-containing starch, and have a DS value of less than 1.5. (For example,
(About 0.3 to 1.3) and a quaternary ammonium salt having antibacterial properties.

The amount of the antibacterial agent carried on the porous carrier can be selected depending on the purpose from the range in which the antibacterial property can be effectively exhibited, for example, 5 to 80% by weight, preferably 10 to 6% by weight.
It is often about 0% by weight (for example, 10 to 50% by weight). If the supported amount is less than 5% by weight, a large amount of antibacterial particles may be required to obtain practically sufficient antibacterial properties.

When the antibacterial powder of the present invention is used by dispersing it in a liquid or the like, it may be surface-treated with a dispersant or the like in order to improve dispersibility.
An additive such as a dispersant may be included.

The loading of the antibacterial agent on the porous carrier is not particularly limited as long as the antibacterial agent can be effectively carried on the porous carrier in the form of a salt. A porous carrier is added to and suspended in an aqueous solution of a polymer. An aqueous solution of a quaternary ammonium salt is added to the suspension, and an antimicrobial agent component (the hydrophilic polymer and the quaternary (A salt with an ammonium salt). Furthermore, after treating the porous carrier with an aqueous solution of a hydrophilic polymer (immersion, impregnation, mixing, spraying, etc.), excess hydrophilic polymer is removed by washing or the like, and the porous carrier is washed with a quaternary ammonium salt. It may be added to and supported on an aqueous solution. The porous carrier carrying the antimicrobial component may be washed with water, dried, or the like, if necessary. (2) First, a salt (an antibacterial agent component) of the anionic hydrophilic polymer and a quaternary ammonium salt is preferably dissolved in a small amount of an appropriate organic solvent (such as methanol) and the like, The antimicrobial agent component is precipitated and supported by mixing the porous carrier and further adding a poor solvent,
It can also be carried out by a method of washing and drying the porous carrier carrying the antibacterial agent with water and the like. Further, (3) the antibacterial agent prepared in advance is dissolved in a soluble organic solvent, or dispersed in water or a poor solvent, and the solution or dispersion is impregnated with or impregnated with a porous carrier. The above solution or dispersion may be sprayed or sprayed. (4) The immobilized quaternary ammonium salt is dissolved in water-containing alcohol (methanol, ethanol, isopropanol, etc.). 15% by weight (preferably 1 to
10% by weight), a porous carrier is added to this solution, mixed, immersed, impregnated, or adsorbed, and then the alcohol aqueous solution is removed by filtration, distillation, evaporation or the like, and dried. , May be obtained. The proportion of water contained in the hydrous alcohol is 0.5 to 50% by weight, preferably 1 to 40% by weight, and particularly about 2 to 30% by weight. When an alcohol containing the above proportion of water is used as the medium, good solubility can be obtained even if the DS value of the quaternary ammonium salt is low, and the ion adsorption power can be increased.

In the above method, the concentration of the aqueous solution of the hydrophilic polymer can be selected according to the viscosity of the aqueous solution of the hydrophilic polymer.
It is about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight (for example, 1 to 2% by weight). The amount of the quaternary ammonium salt is, for example, an amount at which the anionic group in the hydrophilic polymer is completely converted into a salt, for example, with respect to one equivalent of the anionic group (for example, a carboxyl group). , Equivalent amount or slightly excessive amount (about 1 to 1.5 equivalents), preferably about 1.01 to 1.3 equivalents (for example, 1.05 to 1.1 equivalents). Also, the quaternary ammonium salt is advantageously used as an aqueous solution, the concentration of which is, for example,
It is about 10 to 80% by weight, preferably about 20 to 60% by weight (for example, 40 to 50% by weight).

Separation (dehydration) of the salt or the porous carrier carrying the salt is carried out by a conventional method, for example, filtration, decantation,
It can be performed by centrifugation or the like. The precipitate may be purified by a conventional method, but may be washed with water for the purpose of removing by-product sodium chloride and the like.

The antibacterial powder of the present invention can be mixed (stir-mixed, melt-mixed, etc.) with a material to be treated (eg, resin, paint, wall material, concrete, etc.), or coated with an antibacterial powder-particle-containing coating agent. Can be imparted with antibacterial properties by applying to the object to be treated or adding it to pulp or the like to make paper. Furthermore, because it is insoluble or hardly soluble in water or an organic solvent in some cases,
Even when added to water, an organic solvent, or the like, propagation of bacteria and the like can be suppressed without changing the properties. The antibacterial agent used for the powder may be insoluble or hardly soluble in an organic solvent depending on conditions (for example, when using CMC having an average degree of substitution of less than 1.5). In this case, antibacterial properties can be imparted to an object in an environment in contact with the organic solvent.

Since the antibacterial powder of the present invention is a powder in which an antimicrobial agent insoluble or hardly soluble in water is supported on a porous carrier, it is possible to efficiently separate, purify, etc. in the production process. And productivity can be improved. In addition, since the antibacterial powder of the present invention is in the form of fine particles, water and / or an organic solvent (for example, alcohols such as ethanol and isopropanol, ketones such as acetone, aromatic hydrocarbons such as toluene, and the like) ), Etc., it is possible to easily achieve good dispersion in these solvents even if they are insoluble or hardly soluble, and since they are insoluble or hardly soluble in the above-mentioned solvents, such as when coating on a substrate or the like In addition, it is possible to increase the concentration of the coating solution, and furthermore, after coating and drying, elution of the antibacterial agent by the solvent or the like can be suppressed, and stable antibacterial properties can be maintained for a long period of time.

Since the antibacterial powder of the present invention has the above properties, it is useful in applications such as paints, resins, spraying agents, coating agents, building materials (wall materials, concrete, etc.), and papermaking.

[0038]

According to the present invention, an antibacterial agent comprising a salt of an anionic hydrophilic polymer and a quaternary ammonium salt having antibacterial properties is supported on a particulate porous carrier.
Antimicrobial properties can be imparted to various objects. In addition, since the powder is insoluble (poorly soluble) in water or, in some cases, an organic solvent, it can exhibit antibacterial properties even in a liquid, and further suppresses elution of an antibacterial agent component for a long time. Antibacterial properties can be maintained over a long period.

[0039]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. The porous carriers, anionic hydrophilic polymers, quaternary ammonium salts and bacterial strains used in Examples and Comparative Examples are as follows. 1. Porous carrier (a-1): Diatomaceous earth (Glefco Co., Ltd., Variety 6
000) 2. Anionic hydrophilic polymer (b-1): carboxymethyl cellulose (DS: 0.
90) (manufactured by Daicel Chemical Industries, Ltd., purity: 91%) (b-2): carboxymethyl cellulose (DS: 1.
91) (purity 90%, manufactured by Daicel Chemical Industries, Ltd.) 3. Quaternary ammonium salt (c-1): trialkyl (C _1-20 alkyl) benzylammonium chloride (manufactured by Toho Chemical Co., Ltd., benzalkonium salt) Strain (d-1): Staphylococcus aureus
(D-2): Bacillus subtilis IFO 3007 (d-3): Escherichia coli IFO 3301 (d-4): Pseudomonas aeruginosa IFO 344
5) (d-5): Black mold (Aspergillus niger ATCC 6)
275) Examples 1-2 and Comparative Example 1 A 1% by weight aqueous solution of carboxymethylcellulose (CMC) was prepared. While vigorously stirring this CMC aqueous solution,
A 49.7% by weight aqueous solution of a quaternary ammonium salt was added little by little until a quaternary ammonium group became 1.05 equivalent to 1 equivalent of the carboxyl group of CMC, thereby producing a white precipitate. The precipitate is separated from the aqueous layer by centrifugation, washed once with water 20 times the weight of the precipitate using a tank-type washing tank with a stirrer, and then dehydrated again. 2% by weight
30 g of a methanol solution was prepared, 1 g of the porous carrier was immersed in this solution, mixed, and then dried. A glycerin dispersion having a concentration of 10% by weight of this antibacterial powder was prepared. 8. 0.5 mL of the dispersion and a sterilized agar medium (tryptosoya agar medium, manufactured by Nissui Pharmaceutical Co., Ltd.) in a sterilized petri dish
5 mL was dispensed, uniformly mixed, and then solidified to prepare a test plate. About 10 ⁷ cells / mL on the prepared test plate
Inoculate the various test bacterial solutions prepared in Step 1 with a platinum loop.
After culturing at 7 ° C. for 48 hours, the presence or absence of growth of the bacteria was observed and evaluated as the antibacterial performance according to the following criteria. ◎ Bacterial growth is not observed at all. ○ Bacterial growth is hardly observed. × Bacterial growth is observed in large amounts. For comparison, only porous carrier (a-1) which does not carry antibacterial agent is used. The same example was evaluated as described above. The results are shown in Table 1 together with the amount of each component used.

[0040]

[Table 1] As is clear from the table, higher antibacterial properties were obtained in Examples than in Comparative Examples.

Continued on the front page F term (reference) 4C090 AA03 AA07 AA08 BA01 BA04 BA05 BA12 BA13 BA14 BA17 BA24 BA29 BA36 BA41 BA42 BA43 BA44 BA46 BA49 BA50 BA66 BA67 BA68 BA70 BA71 BA72 BA73 BA92 BD36 CA08 CA19 CA35 CA50 DA10 DA21 4H011 AA02BB06 BB08 BB19 BC18 BC20

Claims (16)

[Claims] An antibacterial powder comprising a porous carrier carrying an antibacterial agent composed of a salt of an anionic hydrophilic polymer and a quaternary ammonium salt having antibacterial properties. 2. The antibacterial powder according to claim 1, wherein the porous carrier is composed of inorganic porous particles. 3. The antibacterial powder according to claim 1, wherein the porous carrier is at least one selected from silica, alumina, activated carbon, zeolite, diatomaceous earth, silica gel, perlite and shirasu balloon. 4. The porous carrier has a specific surface area of 0.1 to 300.
^2. The antibacterial powder according to claim 1, wherein the amount is 0 m ² / g. 5. The amount of the antibacterial agent carried on the porous carrier is as follows:
2. The antibacterial powder according to claim 1, which is present in an amount of 5 to 80% by weight. 6. The antibacterial powder according to claim 1, wherein the hydrophilic polymer is a hydrophilic polysaccharide or a hydrophilic resin. 7. The antibacterial powder according to claim 1, wherein the hydrophilic polymer is a water-soluble homoglycan. 8. A hydrophilic polymer comprising carboxyl group-containing cellulose, carboxyl group-containing starch, pectic acid,
The antibacterial powder according to claim 1, which is at least one selected from alginic acid and derivatives thereof. 9. The antibacterial powder according to claim 1, wherein the hydrophilic polymer is a carboxyl group-containing resin. 10. The antimicrobial powder according to claim 1, wherein the hydrophilic polymer is a homo- or copolymer of (meth) acrylic acid. 11. A quaternary ammonium salt represented by the following formula (1): (Wherein, R ^{1 to} R ⁴ are the same or different and each represents a saturated or unsaturated C _1-30 aliphatic hydrocarbon group, an aralkyl group, a mono- or dialkylphenoxy group, an alkyleneoxyalkyl group, a trialkylammoniumalkyl group. either shown, or two or three of R ¹ to R ⁴ may form a hetero ring together with the nitrogen atom. However, at least one saturated or unsaturated C _10-30 of R ¹ to R ⁴ The antibacterial powder according to claim 1, which is an aliphatic hydrocarbon group, wherein X represents a halogen atom. 12. The antibacterial according to claim 11, wherein in formula (1), at least one of R ^{1 to} R ⁴ is a saturated or unsaturated C _10-30 aliphatic hydrocarbon group, and at least one is an aralkyl group. Powder. 13. A porous carrier comprising a salt of at least one type of carboxyl group-containing hydrophilic polymer selected from carboxymethyl group-containing cellulose and carboxymethyl group-containing starch, and a quaternary ammonium salt having antibacterial properties. An antibacterial powder carrying the antibacterial agent, wherein the degree of substitution of carboxymethyl groups per anhydroglucose unit of the hydrophilic polymer is 1.5 or more. 14. A porous carrier comprising a salt of at least one carboxyl group-containing hydrophilic polymer selected from carboxymethyl group-containing cellulose and carboxymethyl group-containing starch, and a quaternary ammonium salt having antibacterial properties. An antibacterial powder or granule carrying the constituted antibacterial agent and having a degree of substitution of carboxymethyl groups per anhydroglucose unit of the hydrophilic polymer of less than 1.5. 15. A method for producing an antibacterial powder or granule, in which a salt in which a quaternary ammonium salt having antibacterial properties immobilized on an anionic hydrophilic polymer is immobilized on a porous carrier. 16. A porous carrier is immersed and dried in an aqueous alcohol containing a quaternary ammonium salt immobilized thereon, and dried.
The method for producing an antibacterial powder according to claim 15, which is carried.