JP2000160027A - Antibacterial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial composition capable of retaining antibacterial properties over a long period of time and, at the same time, excellent in water resistance, weatherability and plane smoothness. SOLUTION: This antibacterial composition is composed of a film formable polymer and an antibacterial polymer, and the antibacterial polymer is a salt of an anionically hydrophilic polymer with a quaternary ammonium salt having antibacterial properties. The film formable polymer is preferably a polymer soluble in an organic solvent. The hydrophilic polymer includes, for example, a hydrophilic polysaccharide such as a water soluble homoglycan and a hydrophilic resin such as a carboxyl group-containing resin. As the quaternary ammonium salt, the one represented by the formula (wherein R1-R4 are the same or different and each a saturated or unsaturated 1-30C aliphatic hydrocarbon group, an aralkyl group, a mono- or dialkylphenoxy group, an alkylene oxyalkyl group or a trialkylammonium alkyl group and two or three of R1-R4 may form a heterocycle with the nitrogen atom; and X is a halogen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial composition useful for imparting high antibacterial properties to an antibacterial film or a coating film, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a water-insoluble or sparingly soluble antibacterial agent has been produced by using a salt of an anionic hydrophilic polymer and a quaternary ammonium salt having antibacterial or antifungal properties. I have.

[0003] Japanese Patent Publication No. 7-14842 discloses that a solution in which quaternary ammonium alginate hardly soluble or insoluble in water is dissolved in an organic solvent or a mixture of an organic solvent and water is applied or impregnated to an object. A method for imparting fungicidal bactericidal properties by using the method is disclosed.

Japanese Patent Application Laid-Open No. Sho 62-56403 discloses a film-forming material (carboxymethylcellulose, gum arabic, alginate, polyacrylate) holding a bactericide mainly composed of polyaminomonocarboxylic acid and benzalkonium chloride. , A dispersant for disinfection containing a simple substance or a mixture of vinyl acetate) and a solvent (water, ethanol, etc.).

JP-A-61-246205 discloses a vinyl monomer having a quaternary nitrogen cation group containing an alkyl substituent having 14 to 20 carbon atoms and a quaternary monomer having an alkyl substituent having less than 14 carbon atoms. A water-dispersible vinyl copolymer obtained by copolymerization with a vinyl monomer having a nitrogen cationic group and an antibacterial composition containing the same are disclosed. In addition, it describes that a monomer such as styrene or acrylic acid may be used in addition to the vinyl monomer in order to control solubility and adhesiveness.

JP-A-1-254605 discloses an antimicrobial composition containing a polymer quaternary ammonium salt which is a reaction product of a homo- or copolymer of acrylic acid or methacrylic acid with a quaternary ammonium salt. Is disclosed. Also,
It is described that a thermoplastic resin such as polyacrylate or polyethylene or a thermosetting resin such as an epoxy resin may be used in combination as a binder.

JP-A-8-113507 discloses an antibacterial agent containing carboxymethylcellulose having a carboxymethyl group substitution degree of 0.4 or more and a silver content of 0.01 to 1% by weight. It is described that the carboxymethylcellulose is crosslinked to make it insoluble in water.

When coating or coating a substrate, these antibacterial agents are usually used by dispersing in water or an organic solvent or dissolving in an organic solvent. However, when these antibacterial agents are applied, application unevenness or the like occurs on the surface of the base material, not only impairing the surface smoothness but also failing to impart the antibacterial properties uniformly. Further, not only the adhesion of the antibacterial coating film, but also the weather resistance and the appearance characteristics are reduced. Further, salts with quaternary ammonium salts have high hygroscopicity, and the water resistance of the coating film is not sufficient.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antibacterial property which can be maintained for a long period of time,
An object of the present invention is to provide an antibacterial composition having excellent weather resistance and a method for producing the same.

[0010] Another object of the present invention is to provide an antibacterial composition which can be applied to a substrate to impart uniform antibacterial properties and form a coating film having excellent surface smoothness, and a method for producing the same. .

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have used an antibacterial composition composed of a polymer capable of forming a film and a specific antibacterial polymer. Then, it was found that the antibacterial property can be maintained over a long period of time, and an antibacterial coating film excellent in water resistance, weather resistance, and surface smoothness can be obtained, and the present invention has been completed.

That is, the antibacterial composition of the present invention comprises a film-forming polymer and an antibacterial polymer,
As the antibacterial polymer, a salt of an anionic hydrophilic polymer and a quaternary ammonium salt having antibacterial properties is used.
The polymer capable of forming a film is usually soluble in an organic solvent such as alcohol. Hydrophilic polymers 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. For example, poly (meta)
Acrylic acid or a derivative thereof). In addition, as the quaternary ammonium salt, a compound represented by the following formula (1) can be used.

[0013]

Embedded image

(Wherein R ^{1 to} R ⁴ are the same or different,
A saturated or unsaturated C _1-30 aliphatic hydrocarbon group, an aralkyl group, a mono- or dialkylphenoxy group, an alkyleneoxyalkyl group, a trialkylammonium alkyl group, or two or three of R ^{1 to} R ⁴ May form a heterocyclic ring together with the nitrogen atom. However, R ^{1 to} R ⁴
At least one is a saturated or unsaturated _C10-30 aliphatic hydrocarbon group. X represents a halogen atom) In the present invention, a salt of an anionic hydrophilic polymer with a quaternary ammonium salt having antibacterial properties and a polymer capable of forming a film are mixed to form an antibacterial composition. Manufacturing methods are also included.

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.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial composition of the present invention comprises a polymer capable of forming a film and an antibacterial polymer, wherein the antibacterial polymer has an antibacterial property with an anionic hydrophilic polymer. It is a salt with a quaternary ammonium salt. [Coating-Formable Polymer] The coating-forming polymer used in the present invention is a resin capable of forming a coating and soluble in an organic solvent such as alcohol, and is preferably a water-insoluble or hardly soluble cellulose-based resin. It is.

Examples of the cellulose-based resin include cellulose esters (eg, organic acid esters such as cellulose acetate, cellulose butyrate, and cellulose propionate; inorganic acid esters such as cellulose nitrate, cellulose sulfate, and cellulose phosphate; cellulose). Mixed esters such as acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate and cellulose nitrate acetate; and cellulose ester derivatives such as polycaprolactone-grafted cellulose acetate; and cellulose ethers (eg, C such as ethyl cellulose and propyl cellulose) _2-10 alkyl cellulose; benzyl cellulose, aralkyl celluloses such as trityl cellulose; cyanoethyl cellulose, Aminoechiruse Loin, such as diethylamino cellulose), and the like. These cellulose derivatives can be used alone or in combination of two or more. The average degree of substitution of the cellulose derivative is, for example, about 0.5 to 3, preferably 1 to 3, and particularly about 2 to 3. The average degree of polymerization of the cellulose derivative is selected from, for example, about 10 to 1000, preferably about 50 to 900, and more preferably about 200 to 800. Preferred cellulose derivatives are cellulose ethers such as ethyl cellulose.

Preferred polymers capable of forming a film include:
Examples include cellulose ethers such as ethyl cellulose and cellulose esters such as acetyl cellulose and cellulose nitrate.

[0019] These resins may be used alone or in combination of two or more.
They may be used together. [Antibacterial polymer] Antibacterial polymer is anionic hydrophilic
A salt of a polymer with a quaternary ammonium salt having antibacterial properties
It is configured. (Anionic hydrophilic polymer) Ani used in the present invention
Quaternary antibacterial as an on hydrophilic polymer
If it can form a salt with ammonium salt, its type is special.
But not limited to, anionic hydrophilic polysaccharides, anio
Hydrophilic resins and the like. The anionic
As the hydrophilic polysaccharide, an anionic hydrophilic group is used in the molecule.
Any polysaccharide (homoglycan, heterog
Lican etc.) can also be used. As the homoglycan
Is a glucan (cellulose, starch, glycogen,
Caronine, laminaran, dextran, etc.), fruta
(Inulin, leban, etc.), mannan (elephant
Xylan (such as rice straw xylan),
Galacturonan (such as pectic acid), mannuronan (such as
Luginic acid), N-acetylglucosamine polymer (ki
And derivatives thereof. Previous
As the heteroglycan, diheteroglycan (guarara)
Konjac mannan, heparin, chondroitin
Sulfuric acid, hyaluronic acid, etc., triheteroglycan (female
Plant gums such as kit gum, gatch gum, gum, fine
Bacterial polysaccharides), tetraheteroglycan (gum arabic)
Such as mucous, rubber, bacterial polysaccharides, etc.) and these
And the like.

The anionic hydrophilic group includes --COO
_{H, -SO 3 H, -OSO 3} H, -H 2 PO 4 , or a derivative thereof, or the like alkali metal salts thereof. Further -NH _2, -CN, -OH, -NHCO
In addition to hydrophilic groups such as NH ₂ and — (OCH ₂ CH ₂ ) —,
_{-NR 3 X, SO 3 NH 2} CO -, - N (SO 3 H) -
(Where R represents an alkyl group and X represents a halogen atom)
And other hydrophilic groups. Preferred hydrophilic groups are carboxyl groups (-COOH) and the like.

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 (CMC), carboxymethylmethylcellulose, carboxymethylethylcellulose, carboxymethylhydroxyethylcellulose, carboxymethylhydroxypropylcellulose, etc.), starch containing a carboxyl group (carboxymethyl starch (CMS), etc.), pectic acid and the like. Derivatives (such as sodium pectate), alginic acid and its derivatives (such as sodium alginate) can be exemplified.

[0022] In the hydrophilic polysaccharide, a quaternary ammonia
Carboxyl groups in the formation of salts with
The amount (average degree of substitution) is not particularly limited, and can be selected according to the application.
For example, 0.3 to 0.3 units per anhydroglucose group
3 (for example, 0.5 to 2.8). Special
When a salt soluble in an organic solvent is desired,
1.3 or more (for example, 1.3 to 3.0), preferably
1.5 or more (for example, 1.5 to 2.8), more preferred
1.6 to 2.8 (for example, 1.7 to 2.5)
You can choose from.

Among the 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).

[0025]

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(Wherein 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 [the degree of carboxymethyl group substitution] (D
S)] is represented by the average degree of substitution of a carboxyl group (carboxymethyl group) per unit of an anhydrous glucose group,
S can be selected from a wide range in which the antibacterial property is not impaired, for example, from about 0.3 to 3 (0.5 to 2.8). In particular, if the salt formed desires a salt that is soluble in an organic solvent, 1.3 or more (e.g., 1.3-3.
0), preferably 1.5 or more (for example, 1.5 to 3.0).
0), more preferably 1.6 to 2.8, especially 1.7 to 2.8.
It is about 2.5. In CMS, the amount of carboxymethyl groups introduced into starch can be selected from the same range as in CMC.

The average degree of polymerization n of CMC is 10 to 1
500 (eg, 50-1500), preferably 100
〜1500 (for example, 400 to 1200).
As the anionic hydrophilic resin, a resin having a hydrophilic group as described above (e.g., a homopolymer or a copolymer of a polymerizable monomer having a hydrophilic group) and the like can be used. Monomer containing a salt thereof (such as styrenesulfonic acid and its sodium salt), and a monomer containing a carboxyl group or a salt thereof (a carboxyl group such as (meth) acrylic acid, crotonic acid, and monoalkyl maleate or a salt thereof) And homo- or copolymers of monomers containing an acid anhydride group (such as maleic anhydride). Further, the anionic hydrophilic resin can also be used as a copolymer of the above-described anionic group-containing monomer and another copolymerizable monomer.

As the copolymerizable monomer, 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. .

The above hydrophilic polymers can be used alone or in combination of two or more. The hydrophilic polymer has a 1% by weight aqueous solution having a viscosity of 10 to 1500 mPa · s, preferably 50 to 1000 mPa · s, more preferably 50 to 50 mPa · s.
It is about 0 mPa · s (for example, 100 to 300 mPa · s). (Quaternary ammonium salt) As the quaternary ammonium salt having antibacterial properties, a compound represented by the following formula (1) can be used.

[0031]

Embedded image

Wherein R ^{1 to} R ⁴ are the same or different,
A saturated or unsaturated C _1-30 aliphatic hydrocarbon group, an aralkyl group, a mono- or dialkylphenoxy group, an alkyleneoxyalkyl group, a trialkylammonium alkyl group, or two or three of R ^{1 to} R ⁴ May form a heterocyclic ring together with the nitrogen atom. However, R ^{1 to} R ⁴
At least one is a saturated or unsaturated _C10-30 aliphatic hydrocarbon group. X represents a halogen atom) In the above formula (1), at least one of R ^{1 to} R ⁴
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 salts include, 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.

[0034] In a preferred quaternary ammonium salt, R ¹ of R ¹ to R ⁴ in 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, etc.). Halogen atom X
Includes fluorine, chlorine, bromine and iodine.

A quaternary ammo having antibacterial properties as described above
Nium salts can be used alone or in combination of two or more.
In constituting the antibacterial composition of the present invention, a particularly preferred antimicrobial composition is used.
Bacterial macromolecules are carboxymethyl group-containing cellulose and
Selected from starches containing carboxymethyl groups
Both have a DS value of 1.3 or more (for example, 1.3 to 2.
8) the antibacterial of the carboxyl group-containing hydrophilic polymer
It is a salt with a quaternary ammonium salt having properties. [Proportion of film-forming polymer and antibacterial polymer] Departure
The antimicrobial composition of Ming
The ratio of the bacterial polymer to the antibacterial polymer is 10 in terms of solid content.
0.1-10 parts by weight of polymer capable of forming a film
0 parts by weight, preferably 0.5 to 50 parts by weight, more preferably
About 1 to 30 parts by weight.

[Additives] The antimicrobial composition of the present invention may contain other additives. Other additives include surfactants, dispersants, plasticizers, lubricants, ultraviolet absorbers, antioxidants, fillers, antistatic agents, coloring agents, fungicides, and other antibacterial agents. You may.

The antimicrobial composition of the present invention is excellent in coatability (workability) on a substrate or the like by combining a polymer capable of forming a film and an antimicrobial polymer, and has uniform and surface smoothness. A high film can be formed. Further, a film having low hygroscopicity and excellent in water resistance and weather resistance can be formed. [Method for producing antibacterial composition] The antibacterial composition of the present invention comprises:
It can be used as a coating agent containing an antibacterial polymer and a film-forming polymer, and the coating agent usually contains an organic solvent.

Examples of the solvent used include alcohols such as methanol, ethanol, isopropanol, butanol and n-pentanol; ketones such as acetone, methyl isobutyl ketone and methyl ethyl ketone; dioxane, diethyl ether, dipropyl ether, tetrahydrofuran and the like. Ethers; esters such as methyl acetate, ethyl acetate and butyl acetate; and cellosolves such as methyl cellosolve ethyl cellosolve and n-propyl cellosolve. It may be used as a mixed solvent.

The polymer capable of forming a film may be a dispersion such as an emulsion. An emulsion-type coating composition containing a polymer capable of forming a film and an antibacterial polymer generally uses water as a solvent.

The solid content concentration of the coating agent is 0.1 to 50% by weight, preferably about 1 to 20% by weight. The antimicrobial composition of the present invention can be prepared by a conventional coating method, for example, brush coating, brush coating, dipping, air knife coating, roll coating,
A gravure coating method, a blade coating method, a dip coating method, a spraying method and the like can be employed. The thickness of the coating film of the antibacterial agent composition is about 0.01 to 500 μm, preferably about 0.1 to 100 μm, and more preferably about 1 to 50 μm.

The antibacterial agent composition of the present invention can be used for various substrates, for example, metal, wood, paper, fiber, nonwoven fabric, plastic molded product, film, sheet and the like.

[0042]

According to the present invention, a uniform film having excellent surface smoothness can be formed by combining a film-forming polymer and an antibacterial polymer, and the antibacterial property can be maintained for a long period of time. Excellent in water resistance and weather resistance.

[0043]

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 film-forming polymers, anionic hydrophilic polymers, quaternary ammonium salts and bacterial strains used in Examples and Comparative Examples are as follows. 1. 1. Polymer capable of forming a film (a-1) Ethyl cellulose (STD-45, manufactured by Dow Chemical Co., Ltd.) Anionic hydrophilic polymer (b-1): sodium carboxymethylcellulose (DS: 1.92, 1% by weight aqueous solution viscosity: 285 mPa
s, moisture: 8.2%, CMC purity: 98%, manufactured by Daicel Chemical Industries, Ltd.) Quaternary ammonium salt (c-1): trialkylbenzyl ammonium chloride (manufactured by Toho Chemical Industry Co., Ltd., benzalkonium salt aqueous solution,
(Purity 49.7%) 4. Solvent (d-1): ethyl alcohol (manufactured by Wako Pure Chemical, purity 9)
(9.6%) 5. Strain (e-1): Staphylococcus aureus
(E-2): Bacillus subtilis IFO 3007 (e-3): Escherichia coli IFO 3301 (e-4): Aspergillus niger ATCC 6
275) Examples and Comparative Examples Carboxymethylcellulose sodium salt (b-1) 4
g was added little by little while stirring with a magnetic stirrer into a 500 mL beaker containing 396 g of pure water and dissolved.

Next, an aqueous benzalkonium salt solution (c-
1) 16.9 g was added little by little with stirring to form a precipitate of carboxymethylcellulose benzalkonium salt, and the precipitate was filtered through a glass filter.
The product in the glass filter was washed with about 400 mL of pure water, filtered, and dried at 105 ° C. for 6 hours to obtain 10 g of carboxymethylcellulose benzalkonium salt.

Next, ethyl alcohol (d-1) 190
Then, 10 g of the above carboxymethylcellulose benzalkonium salt was dissolved in the resulting solution to prepare a 5% by weight solution, and 100 g of the solution was used as a sample solution of a comparative example.

Further, 100 g of this 5% by weight solution
Then, 4 g of ethylcellulose (a-1) was dissolved in the solution to obtain a sample solution of Example. (Antibacterial performance) 8. The sample solution was diluted to a predetermined concentration in a sterilized petri dish with ethyl alcohol, and 0.5 mL of the diluted sample solution was sterilized with a sterilized agar medium (tryptosoya agar medium, manufactured by Nissui Pharmaceutical Co., Ltd.). 5 mL was dispensed, uniformly mixed, and then solidified to prepare a test plate.

The number of bacteria was about 10 ⁷ / m on the prepared test plate.
L, inoculate the various test bacterial solutions prepared using a platinum loop,
After culturing at 37 ° C. for 48 hours, the presence or absence of bacterial growth was observed as described below.

The presence or absence of bacterial growth on the test plate was evaluated according to the following criteria. ◎ Bacterial growth was not observed at all ○ Bacterial growth was hardly observed △ Bacterial growth was observed × Bacterial growth was observed in large quantities-Not evaluated Also, the sample solution was placed on a glass substrate by 10 cm. ^After 0.1 g per ² was cast, dried and allowed to stand for 24 hours, water resistance, weather resistance and surface condition were evaluated. (Water resistance) The glass plate coated with the sample solution was immersed in pure water for 1 hour, allowed to stand at room temperature for 24 hours, dried, and evaluated by the following standard of touch by hand.

◎ No stickiness and no change in hue ○ Some stickiness but no change in hue △ Some stickiness and slightly white (weather resistance) A glass plate coated with the sample solution was heated at 40 ° C.
After leaving in a constant temperature room for 1 month, the evaluation was performed according to the following criteria.

な し No change in hue ○ Slightly discolored to pale yellow 着色 Pale yellow (Surface condition at the time of coating) The surface condition of the film after coating on the substrate was evaluated according to the following criteria.

◎ Extremely smooth and evenly coated ○ Smooth △ Fine irregularities are observed Tables 1 and 2 show the results.

[0053]

[Table 1]

[0054]

[Table 2]

As is clear from Tables 1 and 2, the examples were all compared with the comparative examples in terms of antibacterial performance, water resistance after coating (coating) on a glass substrate, weather resistance, and planar smoothness (surface state). And the antimicrobial performance can be maintained for a long time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 5/06 C08L 5/06 33/02 33/02 C09D 5/14 C09D 5/14 7/12 7 / 12 A 101/00 101/00 103/00 103/00 105/04 105/04 133/02 133/02 F-term (reference) 4J002 AB01X AB02W AB03W AB03X AB04X AB05X BG01X EN136 GB00 4J038 BA011 BA021 BA022 BA091 BA092 BA111 BA112 BA171 CG031 FA301 GA02 GA07 GA08 NA01 NA03 NA04 NA05 NA06

Claims (13)

[Claims] An antibacterial composition comprising a film-forming polymer and an antibacterial polymer, wherein the antibacterial polymer is an anionic hydrophilic polymer and a second antibacterial polymer. An antibacterial composition which is a salt with a quaternary ammonium salt. 2. The antibacterial resin composition according to claim 1, wherein the polymer capable of forming a film is soluble in an organic solvent. 3. The antibacterial composition according to claim 1, wherein the polymer capable of forming a film is a cellulosic resin. 4. The antibacterial composition according to claim 1, wherein the hydrophilic polymer is a hydrophilic polysaccharide or a hydrophilic resin. 5. The antibacterial composition according to claim 1, wherein the hydrophilic polymer is a water-soluble homoglycan. 6. A hydrophilic polymer comprising a carboxyl group-containing cellulose, a carboxyl group-containing starch, pectic acid,
2. The antibacterial composition according to claim 1, which is at least one selected from alginic acid and derivatives thereof. 7. The antibacterial composition according to claim 1, wherein the hydrophilic polymer is a carboxyl group-containing resin. 8. The antibacterial composition according to claim 1, wherein the hydrophilic polymer is poly (meth) acrylic acid or a derivative thereof. 9. 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 composition according to claim 1, which is an aliphatic hydrocarbon group, wherein X represents a halogen atom. 10. The antibacterial according to claim 9, 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. Composition. 11. An antibacterial composition comprising at least one type of carboxyl group-containing hydrophilic polymer selected from carboxymethyl group-containing cellulose and carboxymethyl group-containing starch, and a cellulosic resin, An antibacterial composition, wherein the hydrophilic polymer is a salt of a quaternary ammonium salt having antibacterial properties, and the degree of substitution of carboxymethyl groups per anhydroglucose unit of the hydrophilic polymer is 1.3 or more. 12. The content of the polymer capable of forming a film is 0.1% based on 100 parts by weight of the antibacterial polymer in terms of solid content.
The antibacterial composition according to claim 1, wherein the amount is 1 to 100 parts by weight. 13. A method for producing an antibacterial composition by mixing a film-forming polymer and an antibacterial polymer, wherein the antibacterial polymer is an anionic hydrophilic polymer and an antibacterial compound. Using a salt with a quaternary ammonium salt having the formula: