JPH06345602A - Immobilization of agent having antibacterial and mildew-proofing effects on carrier by photochemical reaction and antibacterial and mildew-proofing process using the carrier - Google Patents

Abstract

PURPOSE:To immobilize an agent having antibacterial and mildew-proofing effects on carrier by photochemical reaction and to provide an antibacterial and mildew-proofing process using the carrier. CONSTITUTION:An agent having antibacterial and mildew-proofing activities are immobilized by painting a polymer having azide groups, etc., on the surface of an insoluble carrier, then painting an effective agent for antibacterial and mildew-proofing activities and further radiating light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for covalently bonding a drug effective for antibacterial and antifungal to a carrier by a photochemical reaction, and a antibacterial and antifungal method using the carrier.

[0002]

2. Description of the Related Art Many cases have been reported in which mold generated in the living environment causes microbial infection and seriously affects health, and cases of food stains caused by mold poison.
As a solution to these important problems, in many areas,
A drug effective for bactericidal and mildew prevention is used. For example, in the case of plastics, their production and processing are performed under extremely physicochemically severe conditions. Therefore, there are only a few types of chemicals that can be used for plastics and that are effective against germs and molds. On the other hand, in recent years, in relation to problems such as MRSA, interest in bactericidal and mildew-proofing processing is increasing in the textile industry.
The method of applying antibacterial treatment to fibers includes a kneading method of raw yarn (an antibacterial agent such as zeolite to which silver or the like is added at the stage of fiber production,
A method of kneading and spinning in a fiber stock solution. ) And a post-processing method (method of adsorbing and fixing an antibacterial agent to a fiber, a method of reacting a functional group on the fiber surface with the antibacterial agent, and a method of adhering and fixing the antibacterial agent to the fiber surface with a resin). When the method of kneading the antibacterial agent into the fiber is adopted, as in the case of the plastic, the processing is performed under severe conditions, so that the usable agents are limited. In addition to these, antibacterial and antifungal treatments are applied in many fields such as leather, wood, building materials, paints, adhesives, papers, paints and metal working oils. In any case, it is important to balance the antibacterial and antifungal effect with the safety to the human body.

[0003]

[Problems to be Solved by the Invention] The main performance requirements of antibacterial and antifungal agents are: 1) Easy handling and uniform mixing and dispersion. 2) It has excellent heat resistance and can withstand the processing temperature sufficiently. 3) It exerts a medicinal effect against mold, bacteria, yeast, algae, etc. even in a small amount. 4) It has excellent weather resistance, does not easily flow out, and maintains its medicinal effect for a long time. 5) It is chemically stable, does not hydrolyze, and does not corrode metals. 6) It is highly safe and has little harm to humans and animals in the practical range. 7) It is economical. Is said. In addition to the excellent antibacterial properties of the antibacterial and antifungal agent, it is also extremely important that the above-mentioned performance is satisfied. If these required performances are not satisfied, the product will be discolored and deteriorated during processing, lose its effectiveness, and be subject to microbial damage. That is, there is a problem that the usable antibacterial and antifungal agents are extremely limited due to processing conditions and safety issues to the human body.

[0004]

It is known that a phenyl azide group is covalently bonded to carbon or the like in the vicinity via a nitrene which is a highly reactive intermediate upon irradiation with ultraviolet rays. Further, it is known that 0-nitrobenzyl ester is decomposed by irradiation with ultraviolet light to generate a carboxyl group (Kaoru Yoshimoto: Photopolymer Handbook: Industrial Research Society 1989). Further, as a method of imparting biocompatibility to an artificial organ, a method of modifying the surface of a material (Japanese Patent Application No.
-206573) is known. This method is a method of imparting biocompatibility by covalently binding a protein such as albumin to the surface of the device via an azide group. On the other hand, the inventors of the present invention have already devised a method of binding an antibiotic to a carrier by a photoreaction and applied for the application (filed on May 30, 1993).

The inventor of the present invention devised to apply the ultraviolet irradiation method of the phenylazide group and the ultraviolet irradiation reaction of 0-nitrobenzyl ester to an antibacterial and antifungal method, and the present invention completed. That is, a) A drug having antibacterial and fungicidal properties, which comprises coating a polymer having an azide group on the surface of an insoluble carrier, and then applying a drug effective for antibacterial and antifungal, and further irradiating with light. Immobilization method. b) The surface of an insoluble carrier is coated with 0-nitrobenzyl ester, and after irradiating with light, the carrier is immersed in a buffer solution in which a water-soluble carbodiimide is dissolved, and then a buffer solution in which a drug effective for antibacterial and antifungal treatment is dissolved. A method for immobilizing a drug which is effective for antibacterial and antifungal treatment, which comprises dipping. c) in phosphate buffer, p-azidobenzoyl
An effective antibacterial / antifungal agent characterized by applying a phenylazide group-introduced effective antibacterial / antifungal agent to an immobilized carrier by reacting with oxy succinimide, and then irradiating it with light. Immobilization method. It was discovered that the carrier prepared by using the above is extremely effective for antibacterial and antifungal, and reached the invention of the present invention.

[0006] Examples of the agents effective for antibacterial and antifungal according to the present invention include 1) antibacterial and antifungal agents, 1-substituted imidazoles, imidazolidione derivatives, N
- substituted amides, triazine derivatives, triazole derivatives, compounds having a methylol group and Mechireso group emit formaldehyde _{(R-O-CH 2 -OH} , R-C
_O-NH-CH 2 -OH, etc.), compounds having an electron-withdrawing α-position or active halogen group in the vinyl position (Br-C
_{H 2 CO-CH 2 C 6} H 5, C 6 Cl 5 CN , etc.), compounds having a vinyl group in alpha, the β-position to the electron-withdrawing group,
Compounds having activated NS bonds (compounds having an isothiazolinone ring, N-trihalomethylthio compounds, etc.), zinc borate, zinc chromate, dichlofla
nid tetrachloisophthaloni
trile iodopropytylcarb
amate (IPBC), tetramethylth
iuradisulfide (TMTD), thio
cyanomethylthiobenzothiaz
ole (TCMTD), glutaraldehyde, phenols, quaternary ammonium, chlorhexidine, benzalkonium chloride, sucrose fatty acid ester, α-bromocinnamaldehyde, alkyldiaminoethyl (aminoethyl) glycine / hydrochloride 1,1′- Hexamethylene bis (5- (4-chlorophenyl) biguanide) · hydrochloride, O-phenylphenol, N, N-dimethyl-N ′
-N'-fluorodichloromethylthiosulfamide, P
-Chlorophenyl-3-iodopropargyl formal,
2-n-octyl-4-isothiazolin-3-one, dehydroacetic acid, sodium dehydroacetate, potassium dehydroacetate, sodium sorbate, potassium sorbate,
P-hydroxybenzoic acid alkyl ester, alkyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, alkylamine, alkylamine salt, 3,5-dimethylterahydro-1,3,3
5-2H-thiadiazin-2-thione, N- (fluorodichloromethylthio) -phthalimide, 8-hydroxyquinoline, 8-hydroxyquinoline hydrochloride, P-chloromethaxinol, benzyl-α-bromoacetate, 4
-Alkylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one, 4- (2-
(Hydroxytetradecylamino) ethyl) -7-methyl, 3,6-dihydro-2-H-1,4-diazepine-
5-one, 4-tetradecylaminoethyl-7-ethyl-3,6-dihydro-2H-1,4-diazepine-5-
On, 1,4-bis (bromoacetoxy) -2-butene, (2-pyridylthio-1-oxide) sodium,
Bis (2-pyridylthio-1-oxide) zinc dimethylcarbamate, sorbic acid, sodium sorbate,
Potassium sorbate, chlorocyanoacetamide,

Bromocyanoacetamide, dibromocyanoacetamide, dichlorocyanoacetamide, 1,1
-Dibromo-1-nitropropanol, 1,1-dibromo-1-nitro-2-acetoxypropane, 3-chloro-3-nitro-2,4-pentanediol, 3-bromo-3-nitro-2,4- Pentanediol, diiodomethyl-3-trisulfone, 2-substituted benzanilide,
1,2-benzisothiazolin-3-one, trialkyltin derivative, bistrialkyltin oxide, triphenyltin derivative, p-chlorophenyl-3-iodopropargyl formal, 3-bromo-3-nitropentanediol-2,4 , 2-bromo-2-nitropropanediol-1-3-phenol compound, cresol,
Orthophenylphenol, parachlormetacresol 2- (thiocyanomethylthio) bezozothiazole, organic sulfur compounds, chlorinated aliphatic compounds, organic iodine compounds, besozuimidazole drugs, organic nitrogen halogens, organic nitrogen sulfur compounds, imazalyl hydrochloride , Creosote,
Didecyldimethylammonium chloride compound, p-
Chlorphenoxy- (3-iodo-2-propargyl) oxymethane, 3-ethoxycarbonyloxy-1-bromo-1,2-diiodo-1-propane, 3-iodo-2
-Propenylbutyl carbamate, diiodomethyl-p
-Tolylsulfone, 2,3,3-triiodoallyl alcohol, tribromophenol, p-bromo-2,5
-Dichlorophenol, trichlorophenol, copper naphthenate, zinc naphthenate, N-nitroso-N-cyclohexylhydroxylamine aluminum, N-nitroso-N-cyclohexylhydroxylamine potassium, monochloronaphthalene, 8-oxyquinoline copper, N-methoxy -N-cyclohexyl-4- (2,5-dimethylfuran) carbanilide, 3-isopropoxy-3'-trifluoromethylcarbanilide, N, N'-dimethyl-
N'-phenyl-N '-(dichlorofluoromethylthio) sulfamide, tetrachloroethylthiotetrahydrophthalimide, tetrachloroisophthalonitrile, 2
-Mercaptobenzothiazole, didecyldimethylammonium chloride, 2,4,6-trichlorophenol sodium, 2,4,6-tribromophenol sodium, p-bromo-2,5-dichlorophenol, p-
Chlorphenoxy-3- (iodo-2-propargyl) oxymethane, 3-ethoxycarbonyloxy-1-bromo-1,2-diiodo-1-propene, 3-iodo-2
-Propenylbutyl carbamate, diiodomethyl-p
-Trisulfone, 2,3,3-triiodoallyl alcohol, 2- (4-thiazolyl) benzimidazole, 2
-Thiocyanomethylthiobenzothiazole, 2-mercaptobenzothiazole, N, N-dimethyl-N'-phenyl-N'-dichlorofluoromethylthiosulfamide, N-1,1,2,2-tetrachloroethylthiotera Hydrophthalimide, N- (trichloromethylthio)-
4-cyclohexene-1,2-dicarboximide,
2,4,5,6-Tetrachlore soft nitrile,
2,3,5,6-Tetrachloro-4- (methylsulfonyl) pyridine, 2-n-octyl-4-isothiazolin-3-one, 10,10-oxybisphenoxyarsine, benzalkonium chloride, didecyldimethylammonium Chloride, 2- (4 thiazdyl) b
enzimadale, N (fluorodichlo
romethylthio) -phtalimide,
N-dimethyl-N'-phenol-N'-
(Fluorodichloro-methyl-
io) -Sulfamide, nystatin, amphotericin B, flucytosine, griseofulvin, hydroxystilbamidine isethionate.

2) Antibiotics Actinomycin Ds, Azaromycin Fs, Amphotericin Bs, Erythromycins, Enramycins,
Oleandomycins, aurethricins, kanamycins, amikacins, aminodeoxykanamycins, kanamycins, tobramycins, capreomycins, carzanophyllines, carbomycins, kitasamycins, gramicidins, gramicidin S, griseophytes Rubins, chromomomycin A ₃ , chloramphenicols, gentamicins, colistins,
Cycloserines, sarcomycins, siccanins,
Dibekacins, josamycins, streptomycins, dihydrostreptomycins, streptomycins, spiramycins, acetylspiramycins,
Spiramycins, spectinomycins, cephalosporins C, cephacetrils, cefazolines, cephapyrins, cephalexins, cephaloglysines,
Cephalothins, cephaloridines, ceftezoles,
Cephrazines, daunorubicins, tetracyclines, oxytetracyclines, chlortetracyclines, tetracyclines, demethyltetracyclines, doxycyclines, minocyclines, metacyclines, doxorubicins, trichomycins, nistacins, neocarzinostatins, Novobiocins, Bomycins, Bacitracins, Variotins, Paromomycins, Pimalcins, Pyrrolnitrins, Futidic acids, Fradiomycins, Bleomycins, Penicillins, Amoxicillins, Ampicillins, Oxacillins, Carbenicillins, Cloxacillins , Cyclacillins, Dicloxacillins, Sulbenicillins, Pibmecillinams, Pheneticillins, Phenoxymethylpenicillin Kind, flucloxacillin class,
Propicillins, hetacillins, benzylpenicillins, amorphous penicillins, mezacillins, pentamycins, polymyxin Bs, mitomycin Cs, maridomycin propionate, micamycins, midecamycins, rifampicins, ribostamycins, linco Mycins, clindamycins, lincomycins, glycopeptide antibiotics, etc.

3) Perfume oil Anise, pey, bergamot, boa de rose, kayapto, cananga, cardamom, cassia, cedar wood, henoposi, cinnamon, citronella, clove, cilantro, cubeba, eucalyptus, geranium, juniper,
Lavender, lemon, neroli, orange, origanum,
Oris root, palmaroza, patchouli, peppermint, pettigren, rose, rosemary, sandal wood, sassafras, spike lavender, spearmint,
Sweet Beach, Sime, Verbena, Camphor, Winter Green, Cemenchina, Iran, Iran, etc. 4) Synthetic flavors anethole, anisaldehyde, anthranilic acid, methyl anthranilate, aldehyde C ₈ , aldehyde C ₉ ,
Aldehyde C ₁₀ , Aldehyde C ₁₁ , Aldehyde C
₁₂ , alcohol C ₈ , alcohol C ₉ , alcohol C
_10. Methyl benzoate, acetophenone, valeric acid, amyl valerate, benzyl valerate, butyl valerate, ethyl valerate, geranyl valerate, phenyl ethyl valerate, isobutyl valerate, menthyl valerate, propyl valerate, valerian. Rosinyl acid, citronellyl valerate, benzaldehyde, benzyl alcohol, borneol, bromostyrene, thymol, dabinol, elemisine, phenyl ethyl alcohol, geraniol, hydrocinnamic aldehyde, hydroxycitraneol, heliotropin, terpinyl hydrate, isoamyl・ Alcohol, isovaleric aldehyde,
Isobutyl alcohol, isomenthol, isomentone, isosaflor, carvone, cinnamic aldehyde, cinnamic alcohol, coumarin, kryptal, cuminal, menthol, menthone, methyl eugenol, musk
Amblet, musk xylene, eugenol, ocimene, australol, α-pinene, piberitol,
Piperiton, limonene, linalool, rosinol, safrole, benzyl acetate, bonyl acetate, linalyl acetate,
Darbinol acetate, cymen, amyl salicylate, camphor, cineole, citonellal, citronellal, citronellol, terpineol, α-thujone, vanillin,
α-Ionone, β-Ionone, Geron, etc.

5) Spice-related compounds Phenol, cinnamic acid, benzaldehyde, ω-bromo.
Styrene, salicyl aldehyde, benzcatexy, heliotropin, vanillin, protocatechu aldehyde, etc. 6) Halogen compounds Chloramine B, chloramine T, etc. 7) Peroxide Benzoyl peroxide, benzoyl acetyl peroxide, etc. 8) Organometallic compounds Phenyl mercury chloride, phenyl mercury acetate, phenyl mercury lactate ethanolamine, phenyl mercury cyanamide, etc. 9) Hydrocarbons, tar benzene, pseudo-cumene, naphthalene, gaayacol, cresol, etc. 10) Halogenated hydrocarbon 3-chloro-2-methyl-propene, o-dichlorobenzene, BHC, iodothymol and the like. 11) Nitrated hydrocarbon, chloronitrated hydrocarbon, nitrobenzene, 2,6-dichloro-4-nitroaniline, tetrachloronitrobenzene, o-nitrodiphenyl and the like. 12) Alcohol hexaline, benzyl alcohol, 2-phenoxy ethanol, 2-butyne-1,4-diol, ethylene.
Chlorohydrin etc. 13) Phenol Phenol, alkylphenol (2-methylphenolic acid,
3-methylphenolic acid, o-cresol, 2,3,5-trimethylphenol, p-benzylphenol, hydroquinone, pterstilbene and the like. 14) Chlorophenol o-chlorophenol, trichlorophenol, chlorocresol, 4-chloro3,5-xylenol, 4-chloro-3-methyl 6-isopropylbenzene, p-chloro-o-phenylphenol, hixachlorophenone,
Brominated-β-naphthol and the like. 15) Ether, cyclic ether 1,4-cineol, phenoxyacetic acid, fumarine, cuberine, dehydroacetic acid, dioxane and the like. 16) Aldehyde Hexamine, hexamethylenetetramine, 1,3-dimethylolurea, salicylaldehyde, α-bromocinnamic aldehyde and the like.

17) Ketones Cyclohexanone, Zalysyl, Benzoquinone, Anthraquinone, Chrysarobin, etc. 18) Carboxylic acid, soap Propionic acid, caprylic acid, hydronocarpsic acid, salicylic acid, mandelic acid, resin acid soap and the like. 19) Ester lactone 2,4-dinitro-6- (2-octyl) phenyl crotonic acid ester, ethyl vanillate, benzoic acid-β-
Naphthyl, paraoxybenzoate, etc. 20) acid amide salicylanilide, 3,4′-dibromosalicylanilide, N-trichloromethyl mercaptophthalimide,
3,5-dinilobenzamide and the like. 21) Carbamic acid, aminocarboxylic acid bigon, zectran, 3,5-diaminopropionic acid, Tego and the like. 22) Cyan, nitrile Tetrachloro / isophthalonitrile, anilinomethylenemalondinitrile, etc. 23) amidine, guanidine formethanate, chlordimeform, guazatine,
Chlorhexidine, etc. 24) Quaternary ammonium salts such as benzalkonium chloride and cetylpyridinium chloride. 25) Pyridine, quinoline, acridine sulfapyridine, isonicotinic acid, pyridinium, 2-
Mercaptopyridine-N-oxide, 8-hydroxyquinoline, chlorquinaldol, aminoquinol, cetylpyridinium chloride and the like. 26) Diazine, triazine dimethylylmol, trimethoprim, triforin, cyanuric acid, dilen, dehydroemetine and the like.

27) Pyrrole, imidazole Pyrrole nitrin, noformicin, gliozin, thiazoylbenzimidazole and the like. 28) Oxazole, oxazine diclozoline, benclozoline, moroxidine, tridemorph and the like. 29) Thioxane, Thioxanthone Hycanson and the like. 30) Thioxane, thioxanthone 2,3-dehydro-5-carboxyanilide-6-methyl-1,4-oxatin, hycanson and the like. 31) Thiazole, thiadian benzisothiazolone, mercaptobenzthiazole,
Benzthion, mylon, phenothiazine, etc. 32) thiocyan, isothiocyan methyl isothiocyanate, chloromethyl thiocyanate,
Bonyl thiocyanate etc. 33) Thiourea, thiosemicarbazide thioburet, cibacil and the like. 34) Dithiocarbamate, thiuram disulfide dithiocarbamic acid, ethylenebisdithiocarbamic acid. Dipyrrolidyl thiuram disulfide and the like. 35) Sulfide, sulfoxide, sulfone tetrasul, allicin, tetradifone, thiamphenicol, protomin and the like. 36) Sulfonic acid o-phenol sulfonic acid, ichitiol, etc. 37) Sulfamide o-nitrobenzenesulfamide, methyl violet, rose aniline, red prontozil, diceptal, sulfanilamide, sulfaphenazole, sulfathiazole, sulfathiadiazole, sulfapyridine, sulfadiazine, sulfame Thiomidine,
Sulfamethoxypyridazine etc. 38) Phosphate ester, thiophosphate ester wepsin, menazone and the like. 39) Halogen compound Sodium fluoride, sodium acid fluoride, sodium silicofluoride and the like. Can be considered (some overlap), but is not necessarily limited to these. Examples of the insoluble carrier according to the present invention include fiber, leather, wood, building materials, plastic, concrete, metal, glass, paper, wallpaper, film, rubber, ceramic (including tile and pottery), etc. It is not limited to. In particular, by applying to daily necessities around kitchen, bathroom, etc., food packaging materials, building materials, etc., a comfortable life without mold can be realized. Also,
By applying the present invention to teeth and dental materials, it is also possible to prevent tooth decay.

[0013]

INDUSTRIAL APPLICABILITY The present invention is characterized in that a) a polymer having an azide group is coated on the surface of an insoluble carrier, and then a drug effective for antibacterial and antifungal is applied, and further irradiation with light is carried out. A method for immobilizing a drug which is effective in preventing fungi. b) The surface of an insoluble carrier is coated with 0-nitrobenzyl ester, and after irradiating with light, the carrier is immersed in a buffer solution in which a water-soluble carbodiimide is dissolved, and then a buffer solution in which a drug effective for antibacterial and antifungal treatment is dissolved. A method for immobilizing a drug which is effective for antibacterial and antifungal treatment, which comprises dipping. c) p-azidobenzoylo in phosphate buffer
An effective antibacterial / antifungal agent characterized by comprising applying a phenylazide group-introduced effective antibacterial / antifungal agent to an immobilized carrier by reacting with xy succinimide, and then irradiating it with light. Immobilization method. The present invention relates to an antibacterial and antifungal method using a carrier prepared by using.
According to the present invention, in the conventional kneading method, it is possible to easily covalently bond the temperature-sensitive antibacterial / antifungal agent which could not be applied to the carrier, and as a result, the elution of the antibacterial / antifungal agent from the carrier can be performed. It becomes possible to prevent it. Therefore, it is possible to prevent the emergence of resistant bacteria to the antibacterial / antifungal agent. With the carrier according to the present invention, a comfortable life free of microorganisms such as mold and bacteria can be realized. By applying the present invention to teeth and dental materials, it is possible to prevent tooth decay.

[0014]

EXAMPLES The present invention will be described in more detail by way of examples.
The present invention is not limited to the embodiments.

Example 1 >> i) Synthesis of azidostyrene 5 g of 3-nitrostyrene was suspended in 20 ml of a mixed solution of ethanol and concentrated hydrochloric acid, and SnC was dissolved in ethanol.
l ₃ 2H ₂ O solution was added with vigorous stirring, at room temperature overnight, and allowed to react. The mixture was neutralized with NaOH, solid components were filtered off, and the product was extracted with ether from the filtrate. After drying the ether layer with MgSO ₄ , concentrated sulfuric acid was added to obtain an intermediate. The intermediate was dissolved in 10 ml of 10% sulfuric acid solution and ice-cooled, and a 1N NaNO ₂ aqueous solution was added. Two hours later,
After adding a NaN ₃ aqueous solution and returning to room temperature, the mixture was stirred for 3 hours. Extract with ethyl acetate and extract with 0.1N N
It was washed with an aqueous aHCO ₃ solution and purified water, added MgSO ₄ , and dried. The solvent was distilled off, and the residue was dissolved in a chloroform / hexane (1/4) mixed solvent and purified by a silica gel column. The solvent was distilled off to obtain 3-azidostyrene. ii) Synthesis of azidostyrene-styrene copolymer 1 mol of azidostyrene and 4 mol of styrene were diluted 5 times with benzene, and 0.01 equivalent of N, N'-azobisisobutyronitrile (AIBN) was added. , Degas, seal tube, 6
Polymerization was carried out at 0 ° C. for 4 hours. After allowing to cool, pour into methanol,
The precipitated azidostyrene-styrene copolymer was recovered. The number average molecular weight of the obtained copolymer was 100,000. iii) Manufacture of wash basin on which miconazole (1-substituted imidazoles) and kanamycin were immobilized The azidostyrene-styrene copolymer synthesized by the above method was dissolved in acetone to prepare a 1% solution. This solution was applied to the entire washbasin made of vinyl chloride and dried to form a film of azidostyrene-styrene copolymer. The above treated basin was immersed in a mixed solution of miconazole / kanamycin dissolved in a phosphate buffer at a ratio of 1% for 1 hour to adsorb miconazole and kanamycin and irradiated with ultraviolet rays for 1 minute using a high pressure mercury lamp. . Next, the washbasin was washed with purified water and dried.

Example 2 >> Miconazole and kanamycin-immobilized washbasin test Example 1 The miconazole- and kanamycin-immobilized basin prepared in 1. was left in the bathroom for 3 months without use. During that time, the bathroom was used by four people daily for a total of about four hours. Washbasin not subjected to the above treatment,
It was left for the same period under the same conditions. During that time, the bathrooms other than the bathtub and floor were not washed at all. About one month later, the bathroom is Pseudomonas aerugin
osa , Pseudomonas diminuta ,
Pseudomonas vesicularis , M
ethlobacterium extorquen
s , Xanthomonas maltophili
a , Asperglus niger , Coryne
Bacterium spp. Started to be covered with, and after 3 months, the entire bathroom except the bathtub and floor was covered. The untreated basin was also covered with the bacteria, but no bacterium was detected in the treated basin.

Example 3 >> i) Synthesis of azidobenzoyloxyethyl methacrylate p-azidobenzoic acid 10 g was dissolved in N, N-dimethylformamide (DMF) 100 ml, ice-cooled, triethylamine 8.5 ml was added, and further isobutyl chloroformate 8.3 ml. Was added. Next, 52 ml of hydroxyethyl methacrylate was dissolved in 300 ml of DMF, added to the solution, and stirred at 60 ° C. for 5 hours. The solvent was evaporated, ethyl acetate was added, extraction was performed, and the mixture was washed with 10% citric acid aqueous solution, purified water, 4% NaHCO ₃ aqueous solution in that order, anhydrous NaSO ₄ was added, and dried. After the solvent was distilled off, the residue was dissolved in chloroform and purified with a silica gel column. The solvent was distilled off to obtain azidobenzoyloxyethyl methacrylate. ii) Azidobenzoyloxyethyl methacrylate-
Synthesis of Methyl Methacrylate Copolymer 1 mol of azidobenzoyloxyethyl methacrylate synthesized by the above method and methyl methacrylate 4
mol and 2-fold diluted with DMF, and 0.01 equivalent of AI
BN was added, degassed, sealed in a tube, and polymerized at 60 ° C. for 3 hours.
After cooling, it was poured into a large amount of ethyl ether to obtain a precipitated azidobenzoyloxyethyl methacrylate-methyl methacrylate polymer. The number average molecular weight of the obtained copolymer was 150,000. iii) Treatment of bathroom with antibacterial / antifungal agent The azidobenzoyloxyethylmethacrylate-methylmethacrylate copolymer synthesized by the above method was dissolved in acetone to prepare a 1% solution. This solution was applied to the entire bathroom (including the bath) and dried to form a film of azidobenzoyloxyethyl methacrylate-methyl methacrylate copolymer. Polymyxin B dissolved in phosphate buffer at a ratio of 1% each in the treated bathroom.
After applying the mixed solution of chlorhexidine / streptomycin / malachite green, and adsorbing the mixed solution of polymyxin B / chlorhexidine / streptomycin / malachite green, ultraviolet rays of 1 are emitted using a high pressure mercury lamp.
Irradiated for minutes. Next, the bathroom was washed with tap water and dried.

Example 4 >> Antibacterial and antifungal effect of bathroom treated with antibacterial and antifungal agent Example 3 The four people used the bathroom treated with the antibacterial and antifungal agent at 4 days daily for 3 months in total. in the meantime,
The bathroom including the bathtub was not washed at all. After 3 months, the bath including the bath was not covered with fungus or mold, but the bath was soiled with scale.

Example 5 >> Preparation of polyethylene cutting board with amikacin and cinnamic aldehyde immobilized By radical polymerization, terpolymer of 2- (4-azidobenzoyloxy) ethyl methacrylate: styrene: o-nilobenzyl acrylate (molar ratio of 3: 6:
1) (hereinafter PASN) was synthesized. The PASN was applied to a polyethylene cutting board to form a thin film, and then ultraviolet rays were irradiated. Next, the polyethylene cutting board is immersed in a phosphate buffer containing a water-soluble carbodiimide,
The reaction was carried out at room temperature for 30 minutes. Subsequently, each was immersed in a phosphate buffer containing 2% amikacin and cinnamic aldehyde, and reacted at 37 ° C. for 8 hours. Next, the polyethylene cutting board was washed with a 1 M NaCl aqueous solution and a phosphate buffer.

Example 6. >> Evaluation of the effect of the polyethylene cutting board which has been subjected to antibacterial and antifungal treatment The polyethylene cutting board prepared in Example 5 was treated with 1N Na.
After the treatment with the OH solution, it was thoroughly washed until the pH of the washing solution became neutral. By aseptic operation, Pse the cutting board
udomonas aeruginosa , Asper
gillus niger , Staphylococc
Us aureus culture, 1 ml each (1 x 1 each
0 ⁸ / ml) was applied and dried, after covering with plastic wrap, 37 ° C.
Incubated for 72 hours in a rotten egg maker. A polyethylene cutting board which was not subjected to antibacterial and antifungal treatment was also coated with the bacterial solution in the same manner and cultured in a 37 ° C. rotator for 72 hours. As a result, the surface of the polyethylene cutting board, which is not subjected to antibacterial and mildew proofing,
Although the above-mentioned bacterial growth was observed, no bacterial growth was observed on the surface of the polyethylene cutting board which had been subjected to antibacterial and antifungal treatment.

Example 7. >> i) Synthesis of Polymer Homopolymer of azidostyrene, 2- (4-azidobenzoyloxy) ethyl methacrylate / styrene / o-
Nitrobenzyl acrylate tripolymer (molar ratio 3: 6: 1) (hereinafter PASN) and N, N'-dimethylacrylamide / o-nitrobenzyl acrylate (hereinafter NIDM) copolymer were each synthesized by radical polymerization. . ii) Preparation of vancomycin and teicoplanin-immobilized non-woven fabric.
After coating and drying ASN, it is irradiated with ultraviolet rays and reacted with a water-soluble carbodiimide in a phosphate buffer, then vancomycin and teicoplanin are added to the buffer at a ratio of 1% each, and the mixture is reacted at 4 ° C for 8 hours. Let The nonwoven fabric subjected to the same operation was washed with a 1M NaCl solution and a phosphate buffer.
After drying, Staphylococcus aureus
The performance was evaluated by the sprinkling method using a (methicillin-resistant) culture solution. As a result, the number of bacteria in the antibacterial non-woven fabric after 24 hours was all 10 or less. On the other hand, on the surface of the non-woven fabric which was not subjected to antibacterial treatment, bacterial growth was observed (8.7 × 10 ⁵ ).

Example 8. Preparation of Denture Covalently Bonded with Cetylpyridinium Chloride A denture prepared by heating and compressing a polyether sulfone resin was covalently bonded with cetylpyridinium chloride by the azidostyrene-styrene copolymer method shown in Example 1. For the denture, Streptococcus
Mutants culture solution 1 ml (1 × 10 ⁸ / ml)
Was dried and cultivated in a rotator at 37 ° C for 24 hours. As a control, the same operation was performed on a polyether sulfone resin denture to which cetylpyridinium chloride was not covalently bonded. As a result, in the denture treated with cetylpyridinium chloride, no growth of bacteria was observed, whereas the surface of the denture not treated was covered with bacteria.

Example 9. >> Preparation of antibacterial HEPA filter and confirmation of antibacterial effect HEPA (High Efficiency Part)
In accordance with the method of Example 3, on the primary surface of the filter medium (made by Nippon Air Filter Co., Ltd.)
Trabecular aldehyde, hinokitiol, colistin and streptomycin were covalently bonded. Regarding the HEPA filter and the HEPA filter not subjected to antibacterial treatment, Pseudomonas aeruginosa ,
Aspergillus niger , Staphyl
ococcus aureus , E. The performance was evaluated by the sprinkling method using E. coli . as a result,
The number of bacteria in the antibacterial HEPA filter after 24 hours was all 10 or less. On the other hand, HE without antibacterial treatment
The number of bacteria on the PA filter was 3.7 × 10 ⁶ , 2.4.
It was x10 < ⁴ >, 8.7x10 < ⁵ >, 4.4 * 10 < ⁵ >. The pressure loss and collection rate of the antibacterial HEPA filter were not different from those of the antibacterial HEPA filter.

Claims (5)

[Claims] 1. An effective antibacterial and antifungal characterized by applying a polymer having an azide group to the surface of an insoluble carrier, and then applying a drug effective for antibacterial and antifungal, and further irradiating with light. Method of immobilizing drug. 2. The surface of an insoluble carrier is coated with 0-nitrobenzyl ester, and after irradiating with light, the carrier is dipped in a buffer solution in which a water-soluble carbodiimide is dissolved, and a drug effective for antibacterial and antifungal is dissolved. A method for immobilizing a drug effective for antibacterial and antifungal treatment, which comprises immersing in a buffer solution. 3. A p-azidobe in a phosphate buffer.
An effective antibacterial and antifungal agent characterized by applying a phenylazide group-introduced effective antibacterial and antifungal agent to an immobilized carrier by reacting it with nzoyloxy succinimide. Immobilization method. 4. An insoluble carrier to which a drug effective for antibacterial and antifungal is covalently bound by the method according to claim 1, 2, or 3. 5. An antibacterial and antifungal method using an insoluble carrier, to which a drug effective for antibacterial and antifungal is covalently bound by the method according to claim 1, 2, or 3.