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WO2003066192A1 - Agent de piegeage de micro-organismes - Google Patents

Agent de piegeage de micro-organismes Download PDF

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Publication number
WO2003066192A1
WO2003066192A1 PCT/JP2003/001322 JP0301322W WO03066192A1 WO 2003066192 A1 WO2003066192 A1 WO 2003066192A1 JP 0301322 W JP0301322 W JP 0301322W WO 03066192 A1 WO03066192 A1 WO 03066192A1
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Prior art keywords
group
microorganism
capturing
saturated
unsaturated
Prior art date
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PCT/JP2003/001322
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English (en)
Japanese (ja)
Inventor
Shuichi Sugawara
Original Assignee
Asahi Kasei Kabushiki Kaisha
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Filing date
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Application filed by Asahi Kasei Kabushiki Kaisha filed Critical Asahi Kasei Kabushiki Kaisha
Priority to JP2003565612A priority Critical patent/JP4522707B2/ja
Priority to AU2003207181A priority patent/AU2003207181A1/en
Publication of WO2003066192A1 publication Critical patent/WO2003066192A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/082—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C12N11/096—Polyesters; Polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • the present invention relates to a microorganism capturing agent. More specifically, the present invention relates to a compound having at least two carboxyl groups, a benzotriazole-based compound, an amide-based compound, a water-insoluble azo compound, and a fourth compound having a specific structure.
  • the present invention relates to a microorganism capturing agent comprising at least one compound selected from the group consisting of a quaternary ammonium salt and a quaternary ammonium salt-containing polymer having a specific structure.
  • the microorganism-capturing agent of the present invention not only has excellent microorganism-capturing ability, but also can maintain such excellent microorganism-capturing ability for a long period of time. It can be used effectively for trapping.
  • microorganism-capturing agent of the present invention is soluble in an organic solvent and Z or a water-containing organic solvent, a microorganism-capturing compound comprising a carrier on which the capturing agent is carried using a solution of the microorganism-capturing agent. Coalescence can be manufactured easily.
  • the complex for capturing microorganisms using the microorganism capturing agent of the present invention can be advantageously used as a carrier for holding microorganisms and Z or bacterial cells in a bioreactor and a biosensor.
  • microbe capture agents substances that have the ability to trap microorganisms used in microbe removal materials for water treatment and bioreactors and as carriers for holding Z or bacterial cells. It has been done. Microbial scavengers are primarily intended for use in water, so they must be water-insoluble to prevent the eradication of the microbial scavengers from attenuating the effect of removing microorganisms over time. I was For example, Japanese Patent Publication No. 62-41641 discloses an insoluble microbial scavenger composed of cross-linked polyvinyl pyridinum halide.
  • microorganism trapping agent disclosed in this publication has a problem that the amount of microorganisms adsorbed by crosslinking for insolubilization decreases.
  • the present inventors have made intensive studies to develop such an excellent microorganism capturing agent as described above.
  • compounds having at least two hydroxyl groups, benzotriazole compounds, amide compounds, water-insoluble azo compounds, and quaternary ammonium salts having a specific structure And at least one compound selected from the group consisting of quaternary ammonium salt-containing polymers having a specific structure.
  • microorganism-capturing agent is soluble in an organic solvent and Z or a water-containing organic solvent
  • a solution of the microorganism-capturing agent is used to form a microorganism-capturing complex including a carrier on which the capturing agent is supported. It has been found that it can be easily produced, and that the obtained composite for capturing microorganisms can be advantageously used as a carrier for holding microorganisms and / or cells in bioreactors and biosensors.
  • the present invention has been completed based on these findings. Therefore, one of the objects of the present invention is not only to have an excellent ability to capture microorganisms, but also to maintain such an excellent ability to capture microorganisms for a long period of time. Agent.
  • Another object of the present invention is to provide a microorganism capturing complex carrying the microorganism capturing agent.
  • Still another object of the present invention is to provide a method for capturing a microorganism by bringing the microorganism capture agent into contact with a liquid or a gas containing a microorganism.
  • Still another object of the present invention is to provide a method for capturing microorganisms by bringing the complex for capturing microorganisms into contact with a liquid or a gas containing the microorganisms.
  • a compound having at least two hydroxyl groups a benzotriazole-based compound,
  • R 1 , R 2 and R 3 are each independently saturated or unsaturated
  • C i _ C 5 Saturated or unsaturated C i -C 5 containing an aliphatic hydrocarbyl group or a hydroxyl group. Aliphatic hydrocarbyl groups, C 6 —C 5 .
  • X represents an ion selected from the group consisting of a thiophene, a logenide ion, an alkyl sulfonate ion, an aromatic sulfonate ion, a sulfate ion and a nitrate ion.
  • R 4 is a nitrogen-containing compound that forms an ammonium ion by bonding to a CH 2 — group on the side chain of the polymer chain, and includes pyridin 4 —dimethylaminopyridine, 2,4 ′ 6 —collidine , 2,3,5—a nitrogen-containing compound selected from the group consisting of collidine, tri (saturated or unsaturated C 3 —Ci 8 aliphatic hydrocarbyl) amine, and quinoline;
  • k and ⁇ are integers that satisfy the following conditions
  • R 5 is a nitrogen-containing compound which forms an ammonium ion by bonding to a CH 2 — group of a side chain of the polymer chain, and includes pyridin 4-dimethylaminopyridinine, 2,4,6-collidine, 2,3,5—Nitrogen-containing compounds selected from the group consisting of collidine, tri (saturated or unsaturated C 3 —C 8 aliphatic hydrocarbyl) amines, and quinoline;
  • R 6 represents a hydrogen atom or a C 1 -C 3 alkyl group
  • Y is a hydrogen atom, a saturated or unsaturated C i -C 5 .
  • Fatty acid residues, C 6 —C 5 Represents an aryl group, a benzyl group, and a sulfoxyl group,
  • a microbial scavenger comprising at least one compound selected from the group consisting of:
  • R 1 , R 2 and R 3 are each independently saturated or unsaturated C 1 C 5 .
  • Aliphatic arsenide de Rokarubiru group containing a hydroxyl group, a saturated or unsaturated C i - C 5.
  • Aliphatic hydrocarbyl groups C 6 —C 5 .
  • X- represents an ion selected from the group consisting of a halide ion, an alkylsulfonic acid ion, an aromatic sulfonic acid ion, a sulfate ion and a nitrate ion.
  • R 4 is a nitrogen-containing compound that forms an ammonium ion by bonding to a CH 2 — group on the side chain of the polymer chain,
  • k and ⁇ are integers that satisfy the following conditions
  • R 5 is a nitrogen-containing compound that forms an ammonium ion by bonding to a C 2 — group on the side chain of the polymer chain,
  • R 6 represents a hydrogen atom or a C 3 alkyl group
  • X— represents a halide ion
  • Y is a hydrogen atom, saturated or unsaturated C 1 -C 5 .
  • Aliphatic carbyl radical saturated or unsaturated C 1 -C 5 .
  • Aliphatic hydrolability Rubiroxy group (saturated or unsaturated C 1 -C 5 .
  • Carboxyl group a saturated or unsaturated CC 50 fatty acid residue, C 6 —C 5 .
  • n and n are integers satisfying the following conditions.
  • R 3 is as defined in the formula (1).
  • the quaternary ammonium salt of the formula (1) is a quaternary ammonium chloride represented by the following formula (6), and a quaternary ammonium salt represented by the following formula (7): And a quaternary ammonium night rate represented by the following equation (8):
  • the polymer represented by the formula (4) is a polymer represented by the following formula (9): 2.
  • R is a saturated or unsaturated C i one C 5.
  • Aliphatic hydrocarbyl A saturated or unsaturated mono-C 5 Q aliphatic hydrocarbyl group containing a hydroxyl group, C 6 -C 5 .
  • r and s are integers satisfying the following relationship.
  • the weight average molecular weight of the polymer of the formula (2) is from 1,000 to 1,000,000.
  • microorganism according to any one of the above items 1, 2 and 4, wherein the polymer of the formula (3) has a weight average molecular weight of 1,000 to 1,000,000. Capture agents.
  • the compound having at least two carboxyl groups is Ethylenediaminetetraacetic acid, cunic acid, hydroxyshethylethylenediaminetriacetic acid, dihydroxylshethylethylenediaminediacetic acid, 1,3 propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and triethyleneethylenetetraacetic acid 2.
  • R 7 is a saturated or unsaturated C _ C 5 .
  • Aliphatic arsenide Dorokarubiru group containing a hydroxyl group, a saturated or unsaturated C i one C 5.
  • Aliphatic hydrocarbyl groups C 6 —C 5 .
  • Ariru group a benzyl group, a saturated or unsaturated C one C 5. Represents a fatty acid residue or a saturated or unsaturated fatty acid ester residue,
  • a microorganism capturing complex comprising a carrier carrying the microorganism capturing agent according to any one of the above items 1 to 9, wherein the weight of the microorganism capturing agent is 0 to the weight of the carrier. 0.1 to 20% by weight of the complex for capturing microorganisms.
  • the carrier comprises a polyester, a polyacrylic acid or a derivative thereof, a polyamide, a polyvinylidene chloride, a polyvinylidene fluoride, a polyurethane, a polysaccharide, a polyoxyalkylene, and a polyoxyalkylene.
  • the microorganism capturing complex according to the above item 10 wherein the complex is produced from at least one compound selected from the group consisting of ethylene terephthalate.
  • a method for capturing microorganisms comprising the following steps (1) and (2).
  • microorganisms are captured by bringing the microorganism capture agent into contact with a liquid or a gas containing the microorganisms.
  • a method for capturing microorganisms comprising the following steps (1) and (2).
  • a composite for capturing microorganisms according to any one of (10) to (13) above.
  • R 4 is a nitrogen-containing compound which forms an ammonium ion by bonding to a CH 2 — group on the side chain of the polymer chain,
  • 3, 5 a nitrogen-containing compound selected from the group consisting of collidine, tri (saturated or unsaturated C 3 _C 8 aliphatic hydrocarbyl) amine, and quinoline;
  • X represents a halide ion
  • k and ⁇ are integers satisfying the following conditions.
  • hydrocarbyl group refers to a monovalent group derived from hydrocarbon
  • IUPAC International Union of Pure and Applied
  • the microorganism capturing agent of the present invention includes a compound having at least two carboxyl groups, a benzotriazole-based compound, an amide-based compound, a water-insoluble azo compound, and a quaternary compound having a specific structure described below. It includes at least one compound selected from the group consisting of an ammonium salt and a quaternary ammonium salt-containing polymer having a specific structure described below.
  • the use of the microorganism capturing agent of the present invention enables capturing while maintaining the active state of the microorganism.
  • the active microorganisms are, for example, microorganisms having a sewage purification ability (ie, activated sludge bacteria).
  • Examples of the compound having at least two propyloxyl groups include, for example, ethylenediaminetetraacetic acid, citric acid, and hydroxyethylethylenediamine.
  • the microorganism capturing agent had to be insoluble in water.
  • the present inventor has reported that, despite the fact that the above-mentioned carboxyl group-containing compound used in the present invention is water-soluble, the microorganism-capturing complex comprising the above-described compound supported on a carrier has excellent microorganism-capturing ability. It has been found that it is possible to maintain such excellent microorganism-capturing ability over a long period of time, in addition to exerting the same. Although the reason is not clear, it is considered to be as follows.For example, when using the above-described complex for capturing microorganisms to capture microorganisms in wastewater or sewage, organic molecules are present on the surface of the complex.
  • microorganisms are adsorbed on the surface of the denatured complex, and the microorganisms are further adsorbed on the microorganisms adsorbed on the carrier.
  • the microorganism-capturing agent of the present invention is used, even if the microorganism-capturing agent is detached from the carrier during the microorganism-capturing treatment, the amount of adsorbed microorganisms from several days to about one week after the start of the treatment
  • benzotriazole-based compounds have And those used as agents.
  • benzotriazole compounds include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-13,1t-butyl-5 , -Methylphenyl) 1 5 —Cro-benzotriazole, 2 — (2'-Hydroxy 5'-t-Butylphenyl) benzotriazole, 2 ⁇ (2'Hydroxy-1 3 ', 5 '—Di-tert-butylphenyl) benzotriazole, 2 — (2'-hydroxy 3', 5 '-di-t-butylphenyl) 1 5 —Cross-opening benzotriazole and (2 '— Hydroxy 3', 5 '-di-t-amylphenyl) benzotriazole, preferably 2 — (2' -hydroxy 3 '-t-butyl-5' -methylphenyl)
  • benzotriazole-based compound interacts with the positively charged part of the skeletal molecule benzotriazole and the negative charge on the cell surface of the microorganism.
  • amide-based compounds examples include those conventionally used as antistatic agents.
  • Preferred specific examples of the amide compound include an N, N-di (polyoxyethylene) -substituted amide amide compound represented by the formula (11).
  • R 7 is a saturated or unsaturated C 1 C 5 .
  • Aliphatic arsenide Dorokarubiru group containing a hydroxyl group, a saturated or unsaturated (E one C 5 aliphatic arsenide Dorokarubiru group, C 6 -.. C 5 ⁇ Li Ichiru group, a benzyl group, a saturated or unsaturated C i one C 5. represents a fatty acid residue or a saturated or unsaturated fatty acid ester residue,
  • the N, N-di (polyoxyethylene) -substituted amide compound represented by the formula (11) has a hydrophobic hydrocarbon moiety and a hydrophilic polyoxyethylene moiety in the R 7 group in the constituent components. Therefore, it exerts a surfactant effect. Therefore, when the N, N-di (polyethylene) -substituted amide compound is coated on the carrier surface, the initial adsorption of microorganisms is promoted by improving the affinity with water on the hydrophobic carrier surface, and the microorganisms are captured. It is considered to be done.
  • water-insoluble 7azo compound examples include those conventionally used as azo pigments.
  • the azo pigment has a wide range of hues, such as yellow, orange, and reddish purple, depending on the combination of the diazo component and the coupling component.
  • Specific examples of azo pigments include Fast Yellow, Disazo Yellow, Disazo Orange, and Naf Examples include tall red.
  • disazo orange one of the water-insoluble azo compounds, has a diazo group and imidazole in the molecule, so when the carrier surface is coated with disazo orange, the surface of the capturing material exhibits a positive charge in water. .
  • the electrostatic interaction between the microorganism and the negatively charged microorganism in water works to capture the microorganism.
  • the quaternary ammonium salt that can be used in the present invention is a compound represented by the following formula (1).
  • R 1 , R 2 and R 3 are each independently saturated or unsaturated C, one C 5 .
  • Aliphatic arsenide Dorokarubiru group containing a hydroxyl group, a saturated or unsaturated C i-C 5.
  • Aliphatic hydrocarbyl groups C 6 —C 5 .
  • Echiru group a benzyl group, a saturated young properly unsaturated C E - C 5.
  • X represents a halide ion, an alkylsulfonate ion Represents an ion selected from the group consisting of aromatic sulfonate, sulfate and nitrate. ).
  • R 1 R 2 and R 3 of the ammonium salt of the formula (1) are each independently saturated or unsaturated C 1 C 2 .
  • Saturated or unsaturated C 1 -C 2 containing an aliphatic hydrocarbyl group or a hydroxyl group.
  • Aliphatic hydrocarbyl group, C 6 -C 2 aryl group, 4 pyridyl group, 2 —dimethylaminoethyl group, 2 — (N —benzyl-NN —dimethylammonium) ethyl group, benzyl group, Saturated or unsaturated C 1 C 2 .
  • fatty acid residue or a saturated or unsaturated fatty acid ester residue is preferably a saturated or unsaturated C—C ester.
  • Saturated or unsaturated C-Ci containing an aliphatic hydrocarbyl group or a hydroxyl group.
  • X— of the ammonium salt of the formula (1) is preferably a chloride ion.
  • the quaternary ammonium salt-containing polymer that can be used in the present invention is a polymer having polymer chains represented by the following formulas (2) to (5).
  • R 4 is a nitrogen-containing compound that forms an ammonium ion by bonding to a CH 2 — group on the side chain of the polymer chain, and is a pyrimidine 4 dimethylaminopyridine, 2, 4, 6 — co lysine, 2, 3, 5 - co lysine, Application Benefits (saturated or unsaturated C 3 - C E 8 fatty Zokuhi Dorokarubiru) ⁇ Mi emissions, and nitrogen-containing Bareru election Ri by Kino Li down or Ranaru group Represents a compound,
  • X represents a halide ion
  • k and ⁇ are integers satisfying the following conditions.
  • R 5 is a nitrogen-containing compound which forms an ammonium ion by bonding to a CH 2 — group on the side chain of the polymer chain
  • 3,5 a nitrogen-containing compound selected from the group consisting of collidine, tri (saturated or unsaturated C 3 —C 8 aliphatic carboxy) amine, and quinoline;
  • R 6 represents a hydrogen atom or a C 1 -C 3 alkyl group
  • X — represents a halide ion
  • Y is a hydrogen atom, a saturated or unsaturated C E - C 5.
  • Aliphatic lipocarbyl group saturated or unsaturated C 1 C 5 .
  • Aliphatic hydrolyl rubyoxy group saturated or unsaturated C 1 C 5 Q aliphatic hydrocarbyl) carboxy group, saturated or unsaturated C 1 C 5 .
  • M and n represent an aryl group, a benzyl group, and a lipoxyl group, and m and n are integers satisfying the following conditions.
  • R 3 is as defined in the formula (1).
  • R 4 in the formula (2) is preferably pyridine, 4-dimethylaminopyridine, or tri (saturated or unsaturated C 3 —C 2 aliphatic lipocarbyl) amine.
  • X_ in the formula (2) is preferably a chloride ion.
  • R 5 in the formula (3) is preferably pyridin, 4-dimethylaminopyridine, or tri (saturated or unsaturated). C 3 —C 2 aliphatic lip mouth carbyl) It is preferred that this be an amiline.
  • R 6 in the formula (3) is preferably a hydrogen atom or a methyl group.
  • X in the formula (3) is preferably a chloride ion.
  • Y in the formula (3) is a saturated or unsaturated C i -C 2 .
  • Saturated or unsaturated C 1 -C 2 containing an aliphatic hydrocarbyl group or a hydroxyl group.
  • Aliphatic arsenide de Rokarubiru group saturated or unsaturated C one C 2.
  • Fat aliphatic arsenide de Rokarubirokishi group saturated or unsaturated C E - C 2 0 aliphatic arsenide de Rokarubi port carboxymethyl
  • carboxymethyl group a saturated or unsaturated C i one C 2. It is preferably a fatty acid residue, a C 6 -Ci 2 aryl group, a benzyl group, or a lipoxyl group.
  • Preferred examples of R 2 and R 3 in equations (4) and (5) are the same as that described above in relation to equation (1).
  • Preferred examples of the quaternary ammonium salt of the formula (1) include a quaternary ammonium chloride represented by the following formula (6): a quaternary ammonium sulfate represented by the following formula (7): , And a quaternary ammonium nitrate represented by the following formula (8):
  • Preferred examples of the polymer of the formula (4) include the following:
  • Preferred examples of the polymer of the formula (5) include the following:
  • R represents a saturated or unsaturated C 1 -C 5 Q aliphatic hydrocarbyl group, a hydroxyl group-containing, saturated or unsaturated 1 -C 5 .
  • Aliphatic hydrocarbyl groups, C 6 —C 5 Represents a aryl group, a benzyl group, a saturated or unsaturated C 5 C fatty acid residue, or a saturated or unsaturated fatty acid ester residue.
  • r and s are integers satisfying the following relationship.
  • R is saturated or unsaturated C—C 5 .
  • C i _ C Aliphatic carboxy group, saturated or unsaturated mono-C 0 aliphatic hydrocarbyl group containing hydroxyl group, C 6 -C 2 aryl group, and benzyl group.
  • a quaternary ammonium salt-containing polymer represented by the formula (9) Can be used, and specific examples thereof include:
  • quaternary ammonium salt-containing polymer represented by the formula (10) known polymers can be used, and specific examples thereof include poly (dimethyl methylene methylene piperidium), dimethyl (trade name: PD- 50; Japan, manufactured by Asahi Denka Kogyo Co., Ltd.).
  • quaternary ammonium salts have a positively charged functional group.
  • the quaternary ammonium salt and the quaternary ammonium salt-containing polymer used in the present invention have an electrostatic interaction with the target microorganism surface. It is presumed that you are doing.
  • the quaternary ammonium salt and the quaternary ammonium salt-containing polymer used in the present invention often have a structure represented by the following formula due to quaternization of the amino group.
  • the quaternized amino group is mainly responsible for capturing the microorganism while maintaining the active state of the microorganism.
  • a compound containing a similar quaternized amino group that does not satisfy the requirements of the present invention such as the cationic surfactant Benzethonium Chloride or chloride Since benzalkonium (Benzalkonium Chloride) is usually used as a bactericidal disinfectant for hulls, it is expected that the quaternized amino group may exhibit a bactericidal action in some cases. Compounds having such a bactericidal action are unsuitable for use as the microorganism capturing agent of the present invention.
  • Japanese Patent No. 3118604 a polyvinylpyridinium halide derivative (Japanese Patent No. 3118604) described as a microorganism-adsorbing resin in Japanese Patent No. 3118604 is also described. It has been reported that it has a bactericidal action (J 0 erg Tiller, Chun—Jen Liao, Kim Lewis, and Ale ander M. K 1 ib anov, Proc. Natl. Acad. Sc i. USA, 9 8, 5981-5985, 2001). On the other hand, the quaternary ammonium salt and the quaternary ammonium salt-containing polymer used in the present invention have a weak bactericidal action against microorganisms and have an excellent trapping action as shown in Examples.
  • the quaternary ammonium salt-containing polymer having the polymer chains represented by the formulas (2) and (3) is prepared by adding 4-vinylpentyl chloride, vinylidene chloride, and a substituted vinyl compound in the presence of a polymerization initiator.
  • a polymerization initiator For example, it is produced by copolymerizing styrene and the like under heating, and then reacting with a base such as pyridine, 4-dimethylaminopyridine, and tertiary organic amine.
  • the quaternary ammonium salt-containing polymer having a polymer chain represented by the formula (2) that can be used is, for example, 4-vinyl benzyl chloride or vinyl chloride as a monomer. Deny (Vinylidene chloride) as a polymerization initiator
  • an equimolar amount of the above It can be obtained by reacting a nitrogen-containing compound (eg, pyridine) in a polar solvent such as ethanol.
  • a nitrogen-containing compound eg, pyridine
  • the reaction conditions for the copolymerization of 4-bibenzylbenzyl chloride with vinylidene chloride are preferably such that the reaction pressure is between atmospheric pressure and 20 atm, and between atmospheric pressure and 1 atm. The pressure is more preferably 0 atm, the reaction temperature is preferably from 180 to 300 ° C, and more preferably from 120 to 80 ° C.
  • the reaction pressure is preferably from atmospheric pressure to 5 atm, more preferably from atmospheric pressure to 2 atm.
  • the reaction temperature is preferably from 0 to 200 ° C., more preferably from 20 to 100 ° C.
  • a quaternary ammonium salt-containing polymer having an it-incorporated chain represented by the formula (3) is, for example, a polymer of 4-bibenzylbenzene as a monomer. Chloride and styrene are copolymerized using a radical initiator such as AI as a polymerization initiator, and then about an equimolar amount of the above-mentioned nitrogen-containing compound with respect to 4-vinylbenzyl chloride (for example, It can be obtained by reacting pyridine in a polar solvent such as ethanol.
  • a radical initiator such as AI as a polymerization initiator
  • the reaction pressure is preferably from atmospheric pressure to 10 atmospheres, more preferably from atmospheric pressure to 2 atmospheres.
  • the reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 ° C.
  • the reaction conditions for reacting the above-mentioned nitrogen-containing compound are preferably a reaction pressure of atmospheric pressure to 5 atm, more preferably atmospheric pressure to 2 atm, and a reaction temperature of 0 to 200 atm. ° C is preferred, and more preferably from 20 to 100 ° C.
  • the number k of monomer units constituting a quaternary ammonium salt-containing polymer having a polymer chain represented by the formula (2) is 10 ⁇ k ⁇ 100, preferably 100 0 ⁇ k ⁇ 1 0, 0 0 0, more preferably 10 ⁇ k ⁇ 5, 0 0 0, ⁇ is 10 ⁇ ⁇ ⁇ 1 0 0, 0 0 0, preferably 1 0 ⁇ ⁇ ⁇ 10 0, 0 0 0, more preferably 10 ⁇ ⁇ 5, 0 0 0. 41.
  • the ratio of vinylbenzyl chloride to pinylidene chloride that is, the ratio of k: ⁇ is preferably in the range of 5:95 to 95: 5, and more preferably 2: 8 to 9: 1. I like it. 4—Better than this range, low percentage of vinylbenzyl chloride provides good microbial capture It is difficult to obtain the performance, and if it is more than this, the water solubility of the obtained copolymer tends to be too high.
  • the number m of monomer units constituting the quaternary ammonium salt-containing polymer having a polymer chain of the present invention represented by the formula (3) is 10 ⁇ m ⁇ 10 0, 00 0, preferably 10 ⁇ m ⁇ 10, 0 00, more preferably 10 ⁇ m ⁇ 5, 0 0, n is 10 ⁇ n ⁇ 1 0 0, 0 0 0, preferably 1 0 ⁇ n ⁇ l 0, 0 0 0, and more preferably 10 ⁇ n ⁇ 5, 0 0 0.
  • the ratio of vinylbenzyl chloride to styrene is preferably in the range of 5:95 to 95: 5, more preferably 2: 8 to 9: 1. preferable. If the proportion of 4-vinylpentyl chloride is smaller than this range, it is difficult to obtain sufficiently good microorganism capture, and if it is larger than this range, the obtained copolymer becomes highly water-soluble. Cheap. '
  • the degree of polymerization of the quaternary ammonium salt-containing polymer represented by the formulas (2) and (3) is preferably 100 or more and 9,000 or less. If the degree of polymerization is less than 100, the water solubility of the obtained polymer tends to increase, and if it exceeds 9,000, the solubility in organic solvents decreases.
  • the weight average molecular weight of the quaternary ammonium salt-containing polymer is preferably from 1,000 to 1,000,000, and the solubility in an organic solvent is high. In consideration of the above, 1, 000 to 50,000, 0000 is more preferable. Even if the molecular weight exceeds 500,000 The microorganism capturing effect of the present invention is achieved.
  • the quaternary ammonium salt-containing polymers represented by the formulas (2) and (3) are contained in a polymer skeleton that does not sufficiently exhibit a microbial trapping effect by itself, although the polymer skeleton itself has excellent chemical stability.
  • various nitrogen-containing compounds such as pyridine, 2,4,6—collidine, 23,5—collidine, 4-dimethylaminopyridine, triethylamine,
  • an amine compound such as triplimamine
  • the surface of the complex for capturing microorganisms prepared by adding or coating the quaternary ammonium salt-containing polymer represented by the above formulas (2) and (3) is positively charged in the aqueous phase. It is thought that there is. As described above, the cell surface of microorganisms is generally negatively charged, and the microorganisms are trapped on the surface of the complex by utilizing the electrostatic interaction between the microorganism and the microorganism trapping agent. (For the state of the surface of the microbial cells, Editor-in-chief: Hisao Morisaki, Hiroyuki Oshima and Kenji Isobe, "Biofilm", published by Science Forum, Japan (1998)). Similarly, cells can be captured on the complex surface.
  • Most of the compounds that can be used as the microbial scavenger of the present invention are soluble in organic solvents having a water content of not more than 20% by weight. It can be dissolved in an organic solvent such as alcohol to form a solution. Therefore, the solution of the microorganism capture agent of the present invention can be impregnated with various carriers, or the solution can be sprayed on the carrier. By performing the coating, the complex for capturing microorganisms of the present invention can be produced.
  • the microorganism capturing agent of the present invention contains the polymer represented by any of the above formulas (2) to (5), the microorganism capturing agent itself may be used as a material or a substrate for producing a carrier for capturing microorganisms. Is possible.
  • THF trifluoroethyl ether
  • DMF dimethylformamide
  • DMA dimethylacetamide
  • Materials used for the carrier of the microorganism capture complex include polyester resins, polyamide resins, polyurethane resins, acrylic resins, polyvinylidene chloride, and polyvinylidene fluoride.
  • Polyoxyalkylene polyoxyalkylene compound, cell Natural polysaccharides such as loin and chitin are used.
  • Polyvinylidene chloride is preferred in view of the durability and chemical stability of the compound and, when used in water, the greater the specific gravity of the fiber made of the compound, the faster it sinks.
  • any material can be used as long as it can form a complex for capturing microorganisms, such as a fiber, a woven fabric, a knitted fabric, a nonwoven fabric, a membrane, a hollow fiber, and a particle. .
  • Examples of the method of applying the microorganism capturing agent of the present invention to the microorganism capturing carrier include a method of impregnating the microorganism capturing carrier with the microorganism capturing agent solution, and coating the microorganism capturing agent solution on the carrier by spraying or the like. And a method in which a microorganism capturing agent is mixed with a carrier raw material, melted, and shaped, and the like.
  • Examples of the form of the composite for capturing microorganisms provided with the microorganism capturing agent of the present invention include fibers, woven fabrics, knitted fabrics, nonwoven fabrics, membranes, hollow fibers, particles, and adsorption carriers constructed based on them. It is preferably used as a woven or knitted fabric.
  • the above-mentioned fibers are usually used as an aggregate obtained by simply combining the fibers, for example, in a state in which short fibers and long fibers are packed in a mesh bag-like or net-like container.
  • the carrier used in the complex for capturing microorganisms of the present invention is preferably a carrier having an ability to adsorb microorganisms.
  • examples of such carriers include polyvinylidene chloride, polyethylene terephthalate, and the like. JP03 / 01322
  • a method for capturing a microorganism by bringing the microorganism capturing agent of the present invention into contact with a liquid or a gas containing a microorganism.
  • liquid containing microorganisms examples include clean water, sewage, industrial water, wastewater, human waste, and the like.
  • gas containing microorganisms include aseptic rooms, clean rooms, hospital rooms, operating rooms, The air used for breeding and cultivation of microbes, pharmaceutical factories, food factories, precision machinery factories, etc. can be mentioned.
  • the microorganism capturing agent used in the method of the present invention is as described above.
  • a specific operation for capturing microorganisms can be performed by a known method.
  • the microorganism capturing agent of the present invention is a polymer represented by the above formulas (2) to (5), a fibrous polymer is used, and the fibrous polymer is formed into a net or a ball. Submerged in water to capture microorganisms.
  • reference can be made to publicly known documents such as “Water Purification Manual-One Technology and Practical Example-” (2001, Kaibundo Shuppan Co., Ltd., Japan).
  • the above-mentioned complex for capturing microorganisms obtained by supporting the above-mentioned microorganism-capturing agent of the present invention on a carrier may be brought into contact with a liquid or gas containing microorganisms to capture the microorganisms.
  • the microorganism capturing complex used in this method is as described above.
  • a specific method for capturing microorganisms can be performed by a known method.
  • the carrier is in the form of fiber, woven fabric, knitted fabric, membrane, hollow fiber, etc.
  • a method of adsorbing on the surface of the fiber or membrane, or in the case of non-woven fabric, filter on the surface of or inside the non-woven fabric There is a method of adsorption by excess.
  • the microorganisms enter the nonwoven fabric and adsorb the microorganisms inside, so that the surface area can be used effectively.
  • the particle form there is a method of adsorbing on the particle surface or inside the particle, and the particle can be used by filling the column or the like with the particle.
  • the capture operation reference can be made to publicly known documents such as the “Environmental Microbial Engineering Research Method” (1993, Gihodo Publishing Co., Ltd., Japan).
  • the microorganism capturing agent of the present invention can be used alone or supported on a carrier and used for capturing microorganisms.
  • the complex for capturing microorganisms of the present invention can be used to improve the ability of the carrier to absorb microorganisms. It can be used as an adsorption carrier. It can also be used as a bioreactor for cell capture and cell fixation.
  • the microorganism capture complex obtained by applying the microorganism capture agent of the present invention to a microorganism capture carrier has a surface with water. It becomes possible to charge positively in the phase and the gas phase.
  • microorganisms to be captured by the microorganism capturing agent and the composite for capturing microorganisms include bacteria, fungi, algae, viruses, activated sludge bacteria, and denitrifying bacteria.
  • microorganisms that also include cells as capture targets are described in, for example, Iwanami Shoten, “Iwanami Biological Encyclopedia, 4th Edition” (issued 4th edition, July 15, 2002, July 15, 2002) in Japan. Refer to the description of the listed biological classification table.
  • bacteria examples include facultative anaerobic bacteria
  • fungi examples include Trichophyton and .Microsporum belonging to incomplete bacteria.
  • Fungi also commonly called molds, are fungi such as black mold of the genus Cladospori umu, blue mold of the genus Aspergilus (Aspergi 1 lus), and blue mold of the genus Penicillium (Penici 1 i um). Is mentioned.
  • algae examples include Microcystis belonging to the class Cyanobacteria and 0 sci 11 a t 0 ria (uremo).
  • Still another object of the present invention is to provide a quaternary ammonium salt-containing polymer represented by the above formula (2).
  • the specific structure of the quaternary ammonium salt-containing polymer and the production method thereof are as described above.
  • This polymer containing a quaternary ammonium salt is a compound that is particularly useful as a microorganism capturing agent.
  • Still another object of the present invention is to provide a quaternary ammonium salt represented by the following formula (12).
  • the quaternary ammonium salt of the above formula (12) is a particularly preferred example of the quaternary ammonium salt of the above formula (1), and is extremely useful as a microorganism capturing agent.
  • the quaternary ammonium salt represented by the formula (12) is obtained by heating benzyl chloride in an equimolar amount or an excess amount (usually 1 to 2 equivalents) with 4-dimethylaminopyridine under a normal pressure in a polar solvent such as ethanol. It is obtained by reacting for several hours to several tens of hours under a temperature of 50 to 80 ° C in the case of an ethanol solvent. NMR confirmed that the reaction site was not a pyridine nitrogen atom but a dimethylamino group nitrogen atom.
  • the solution after the phage capture process is used as the test solution, and a part of the solution is taken and diluted in a phosphate buffer.
  • Each 50 ⁇ of the test solution and the diluent was added to an L ⁇ medium (10 g / kg of Paktotripton, 5 g of yeast extract, 5 g of Zinc, 5 g of NaCl, in distilled water).
  • L ⁇ medium 10 g / kg of Paktotripton, 5 g of yeast extract, 5 g of Zinc, 5 g of NaCl, in distilled water.
  • E. coli JM109 culture solution 200 a ⁇ cultured overnight at 37 ° C at 37 ° C, and allow the resulting mixture to stand at 37 ° C for 10 minutes.
  • Prepare a 3 ml LB soft agar medium (prepared by adding 0.7% by weight of agar in the LB medium), which was previously dissolved and kept at 50 ° C.
  • the PET non-woven fabric with the cells attached is immersed in a methylene blue solution for 2 minutes to stain the cells, and then the excess dye is removed by washing with water, and a certain amount of 10% SDS (sodium dodecy 1 sulfate)
  • SDS sodium dodecy 1 sulfate
  • the dye is extracted by adding the solution to obtain a sample solution.
  • Using a UV-160A spectrophotometer manufactured by Shimadzu Corporation, Japan, measure the absorbance at 660 nm of the sample solution using a 1 cm long quartz cell. Calculate the extinction coefficient at 660 nm from the absorbance according to the following formula.
  • This compound was analyzed by 1 H-NMR analysis using tetramethylsilane as the standard in DMSO (dimethylsulfoxide) -d6 solvent to find that the nitrogen atom of the 4-dimethylamino group was a benzyl group.
  • the adhesion rate of the quaternary ammonium compound to the nonwoven fabric is ⁇ (weight of nonwoven fabric after adhesion / weight of nonwoven fabric before adhesion) / (weight of nonwoven fabric before adhesion) X 100 ⁇ is 1.0% by weight.
  • Met. The microorganism capture complex, after 3 2 stacked packed in a column having an inner diameter of 2 cm, were suspended to a concentration of 5 XI 0 8 pieces / m .1 to saline Eshieri Kia co Li (Escherichia Col [pi Liquid The solution was passed through the column at a rate of 45 m 1 Z hr. The number of viable bacteria in the filtrate obtained by passing through the plate was determined by the agar plate pour method (the 14th revision of the Japanese Pharmacopoeia).
  • the compound of (14) is a DMS with tetramethylsilane as standard. - It was confirmed to be by Ri quaternized Jimechiruami amino group Gabe Njiru group Ri by the 1 H- NMR analysis d 6 solvent. Also, a singlet peak due to dimethyl at ⁇ 3.15, a singlet peak due to ethylene at ⁇ 4.19, a singlet peak due to benzylmethylene at 0.47.66, and ⁇ 55.33 to A peak due to phenyl was observed at 7.70.
  • a carrier for capturing microorganisms was obtained by punching a nonwoven cloth made of PET (0.016 decitex fineness) into 2 cm.
  • the PET nonwoven fabric was impregnated with a THF solution (10 mg / m 1) in which the quaternary ammonium compound was dissolved for 30 seconds, and then dried at room temperature under reduced pressure for 1 hour to obtain a composite for capturing microorganisms.
  • the adhesion rate of the quaternary ammonium compound (14) to the nonwoven fabric was 1.0% by weight.
  • the microorganism capture complex after 3 2 stacked packed in a column having an inner diameter of 2 cm, were suspended to a concentration of 5 XI 0 8 pieces / m 1 in physiological saline Eshieri Kia co Li (Escherichia Col 0 The filtrate was passed through the column at a rate of 45 m 1 Z hr. The viable cell count in the filtrate obtained through the passage was measured over time by the agar plate pour method, and the eradication rate was determined. The results are shown in Table 1.
  • a solution of citrate in THF (10 mg / m2) was added to the same PET non-woven fabric (fineness: 0.016 decitex) as in Example 1. After 1) was impregnated for 30 seconds, it was dried at room temperature under reduced pressure for 1 hour to obtain a microorganism capturing material. The adhesion ratio of citric acid to the nonwoven fabric was 1.0% by weight.
  • the microorganism capture complex after 3 2 stacked filling the column with an inner diameter of 2 cm, are suspended in a concentration of Eshierikia co Li (Escherichia Col i) the saline 5 XI 0 8 pieces / m 1
  • Eshierikia co Li Eshierikia co Li
  • the solution was passed through the column at a rate of 45 m 1 Z hr.
  • the number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. Table 1 shows the results.
  • a PET nonwoven fabric (fineness: 0.016 decitex) similar to that of Example 1 was added with 2— (2′-hydroxyl-3′-t-butyl-5′-methylphenyl) represented by the chemical formula (15).
  • I 5 Carbon-mouth benzotriazole (trade name: JF-79, manufactured by Johoku Chemical Co., Ltd., Japan) dissolved in a THF solution (1 O mg / m 1) for 30 seconds After drying at room temperature under reduced pressure for 1 hour, a complex for capturing microorganisms was obtained.
  • the adhesion rate of the benzotriazole derivative (15) to the nonwoven fabric was about 1.0% by weight.
  • Example 5 After packing the microbe-capturing complex in a two-layer column with a 2 cm inner diameter, the Escherichia Coli was suspended in physiological saline at a concentration of 5 ⁇ 10 8 cells / m 1. The solution was passed through the column at a rate of 45 ml / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. Table 1 shows the results.
  • Example 5 shows the results.
  • a carrier for capturing microorganisms was obtained by punching a nonwoven cloth made of PET (0.016 decitex) into a 2 cm diameter.
  • the PET nonwoven fabric was impregnated with a THF solution (10 mg / m 1) in which the quaternary ammonium salt-containing polymer was dissolved for 30 seconds, and dried at room temperature under reduced pressure for 1 hour to obtain a composite material for capturing microorganisms. I got a body.
  • the adhesion rate of the vinyl copolymer to the nonwoven fabric was 1.0% by weight. there were.
  • the microbial capture complex after 3 2 stacked packed in a column having an inner diameter of 2 cm, are suspended in a concentration of Eshieri Kia co Li (Escherichia Col i) the saline 5 XI 0 8 or Z m 1
  • Eshieri Kia co Li Eshieri Kia co Li
  • the solution was passed through a column at a rate of 45 ml / hr.
  • the number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. Table 1 shows the results.
  • This microorganism capturing complex was applied to a column in the same manner as in Example 1.
  • the Eshierikia co Li Esscherichia Col i
  • the Eshierikia co Li was suspended in a concentration of 5 XI 0 8 or Z m 1 in physiology saline solution was passed through the column at a rate of 4 5 m 1 / hr .
  • the number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. Table 1 shows the results. Comparative Example 1
  • Example 1 Without using the compound of the present invention, only the PET nonwoven fabric of the carrier for capturing microorganisms used in Example 1 was packed in a column, and Escherichia Coli was added to a saline solution at a concentration of 5 ⁇ .
  • Table 1 As can be clearly seen, the microorganism-trapping complex using the nonwoven fabric with the microorganism-trapping agents of Examples 1, 2, 3, 4, 5, 6 and 7 adhered to the bacteria. Excellent power and high eradication rate. In the case of Comparative Example 1 to which the microorganism-capturing agent of the present invention was not adhered, the adsorbing power of the bacterium was weak, and the bacterium was remarkably reduced with the passage of time.
  • the (Staphylococcus aureus) was suspended in a concentration of the saline 3 X 1 0 8 M m 1 solution was passed through the column at a rate of 6 0 m 1 / hr.
  • the number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. The results are shown in Table 2.Comparative Example 2
  • Example 2 Without using a microorganism scavenger of the present invention, only the PET nonwoven microbial trapping carrier used in Example 1 was packed into a column, 3 X 1 0 8 or Sutafi loco Kkasu Aureusu the (Staphylococcus aureus) in saline Bruno The liquid suspended at a concentration of m 1 was passed through the column at a rate of 60 m 1 / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. Table 2 shows the results.
  • Example 1 Without using a microorganism scavenger of the present invention, only the PET nonwoven microbial trapping carrier used in Example 1 was packed into a column, the shoes de 'Sphingomonas Aeriregino one The J seudomonas aeruginosa) with saline 6 XI 0 8 The liquid suspended at a concentration of Zm1 was passed through the column at a speed of 30 m ⁇ / r. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time by the agar plate pour method, and the eradication rate was determined. Table 3 shows the results.
  • the microorganism-trapping complex using the PET nonwoven fabric to which the microorganism-trapping agents of Examples 1, 2, 3, 4, 5, 6, and 7 were attached has a lower absorption capacity for bacteria. Although excellent and good eradication rate was exhibited, Comparative Example 3 to which the microorganism trapping agent of the present invention was not adhered had a weak bacterial adsorbing power, and was significantly improved with time. The eradication rate was only about 8%.
  • Each of the 2 ⁇ microbial capturing complexes produced in the same manner as in Examples 1, 2, 3, 5 and 7 was stacked and packed in 32 pieces on a power ram having an inner diameter of 2 cm.
  • a suspension obtained by suspending an off-phase in physiological saline at a concentration of 5 ⁇ 10 6 particles Z m 1 was passed through the column at a rate of 40 m 1 / hr.
  • the number of phage particles in the filtrate obtained by passing the solution was measured over time by the above method, and the removal rate was determined. Table 4 shows the results. Comparative Example 4
  • examples only PET nonwoven microbial trapping carrier used in 1 was packed into a column, M l 3 bar Kuteriofu ⁇ one di saline 5 XI 0 6 particles Z m
  • the liquid suspended at a concentration of 1 was passed through the column at a speed of 40 m 1 / r.
  • the number of phage particles in the filtrate obtained by passing the solution was measured over time to determine the removal rate. Table 4 shows the results.
  • a 2 cm ci) microbial capturing complex obtained in the same manner as in Examples 1 to 7 was immersed in an activated sludge-containing liquid for 14 hours or 48 hours, and the activated sludge tank was immersed. It was shaken back and forth at a speed of 50 rpm.
  • the cells adhering to the above-described complex for capturing microorganisms were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of adhered cells.
  • Table 5 shows the results.
  • the amount of adhered cells is proportional to the absorbance of methylene blue, and the higher the value of the absorbance (660 nm), the greater the amount of adhered cells is determined. Comparative Example 5
  • Example 1 Without using the microorganism capturing agent of the present invention, only the PET nonwoven fabric used in Example 1 was immersed in a solution containing activated sludge for 14 hours or 48 hours, and the activated sludge tank was rotated at 50 rpm. Shake back and forth. The cells attached to the PET nonwoven fabric were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of the attached cells. The results are shown in Table 5 ⁇ .
  • the microorganism-trapping complex using the PET nonwoven fabric prepared by adhering the microorganism-trapping agents of Examples 1 to 7 is excellent in the ability to capture bacteria, but the microorganism-trapping compound of the present invention. It can be seen that the sample of Comparative Example 5 to which no is attached has a weaker ability to capture bacteria. Table 5
  • the complex for capturing microorganisms of 2 ⁇ produced in the same manner as in Examples 1 to 7 was added to the solution containing denitrifying bacteria for 14 hours or more. It was immersed for 48 hours, and the denitrifying bacteria tank was shaken back and forth at a speed of 50 rpm.
  • the cells adhered to the above-described complex for capturing microorganisms were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of the adhered cells.
  • Table 6 shows the results.
  • the amount of attached cells is proportional to the absorbance of methylene blue, and the higher the value of the absorbance (660 nm), the larger the amount of attached cells is determined. Comparative Example 6
  • Example 1 Without using the microorganism capturing agent of the present invention, only the PET nonwoven fabric used in Example 1 was immersed in a denitrifying bacteria-containing solution for 14 hours or 48 hours, and the denitrifying bacteria tank was rotated at a speed of 50 rpm. Shake back and forth. The cells adhered to the PET nonwoven fabric were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of the adhered cells. Table 6 shows the results.
  • the microorganism-trapping complex using the PET nonwoven fabric prepared by attaching the microorganism-trapping agent of Examples 1 to 7 is excellent in the ability to capture bacteria, but the microorganism-trapping agent of the present invention It can be seen that in the case of Comparative Example 6 where no bacteria were attached, the ability to capture bacteria was weak. Table 6
  • Example 6 (41 mg, 0.25 mmol) was reacted under the same conditions as in Example 6 to obtain a compound obtained by copolymerizing 4-vinylbenzyl chloride and vinylidene chloride at a molar ratio of 1 Z 1. Obtained. The above molar ratio was confirmed by NMR. Next, 4-vinylbenzyl chloride was quaternized with an equimolar amount of pyridine to obtain a quaternary ammonium salt-containing polymer.
  • a carrier for capturing microorganisms was prepared by punching a non-woven fabric made of polyethylene terephthalate (PET) (fineness: 0.016 decitex) into 2 cm ⁇ .
  • PET polyethylene terephthalate
  • the PET non-woven fabric was impregnated with a THF solution (10 mg Zm 1) in which the quaternary ammonium salt-containing polymer was dissolved for 30 seconds, and then dried at room temperature under reduced pressure for 1 hour, to obtain a vinyl-based non-woven fabric.
  • a complex for capturing microorganisms having an adhesion rate of the polymer of about 1.0% by weight was prepared.
  • the microorganism capture complex after 3 2 stacked packed in a column having an inner diameter of 2 cm, were suspended to a concentration of Eshierikia co Li (Escherichia Col i) the saline 5 XI 0 8 pieces / m 1 The liquid was passed through the column at a rate of 45 m 1 / hr.
  • Example 14 Without using the quaternary ammonium salt-containing polymer of the present invention, only the PET non-woven fabric used in Example 13 was packed in a column, and Escherichia Coli was added to a physiological saline solution. The liquid suspended at a concentration of 8 cells / ml was passed through the column at a rate of 45 ml / hr. Table 7 shows the results obtained by measuring the number of viable bacteria in the filtrate obtained by passage over time and determining the eradication rate.
  • Example 14 shows the results obtained by measuring the number of viable bacteria in the filtrate obtained by passage over time and determining the eradication rate.
  • Example 6 (41 mg, 0.25 mmol) was reacted under the same conditions as in Example 6 to give a compound obtained by copolymerizing (4-pinylbenzylchloridnovinylidene chloride) at a molar ratio of 2/3. Obtained. The above molar ratio was confirmed by NMR. Next, in the same manner as in Example 13 except that a quaternary ammonium salt-containing polymer obtained by quaternizing 4-vinylbenzyl chloride with an equimolar amount of pyridine was used. Thus, a complex for capturing microorganisms was obtained.
  • Example 2 After this microorganism capture complex was packed in a column in the same manner as in Example 1 3 was suspended in a concentration of Eshieri Kia co Li (Escherichia Col i) the saline 5 XI 0 8 pieces / m 1 The solution is passed through the column at a rate of 45 ml / hr, and the viable cell count in the filtrate is determined. Table 7 shows the results measured over time.
  • Example 16 After stacking three 2 cm-diameter microorganism-complexes obtained in the same manner as in Example 13 in a 2 cm-diameter column in a stack, Staphylococcus aureus was replaced with physiological saline. water 3 XI 0 8 pieces / m 1 of a liquid suspended in a concentration was passed through the column at a rate of 6 O ml Z hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time, and the eradication rate was determined. Table 8 shows the results.
  • Example 16 shows the results.
  • a 2 cm ⁇ complex for capturing microorganisms obtained in the same manner as in Example 13 was packed in a stack of 32 pieces in a column having an inner diameter of 2 cm, and then packed in a stack.
  • Pseudomonas aeruginosa Pseudomonas aeruginosa
  • aeruginosa was suspended in physiological saline at a concentration of 6 ⁇ 10 8 Zm 1 and passed through the column at a rate of 30 m 1 / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time, and the eradication rate was determined. Table 8 shows the results.
  • Example 6 (41 mg, 0.25 mmol) was reacted under the same conditions as in Example 6 to give a compound obtained by copolymerizing (4-vinylbenzyl chloride Z vinylidene chloride) at a molar ratio of 1 Z 4. I got The above molar ratio was confirmed by NMR. Next, this was quaternized with an equimolar amount of pyridine based on 4-vinylbenzyl chloride to obtain a quaternary ammonium salt-containing polymer. A composite for capturing microorganisms was obtained in the same manner as in Example 13 except that the obtained quaternary ammonium salt-containing polymer was used.
  • Example 19 4-vinylylbenzodiolechloride (3.82 g, 25 mmol), vinylidene chloride (2.12 g, 125 mmol) and AIBN
  • Example 6 (41 mg, 0.25 mmol) was reacted under the same conditions as in Example 6 to give a compound in which 4-vinylbenzyl chloride and vinylidene chloride were copolymerized in a molar ratio of 1 Z 1. I got The composition ratio was confirmed by NMR. Next, 4-vinylbenzyl chloride was quaternized with an equimolar amount of pyridine to obtain a quaternary ammonium salt-containing polymer.
  • a PET non-woven fabric is impregnated with a THF solution (10 mg Zml) in which the above quaternary ammonium salt-containing polymer is dissolved for 30 seconds, and then dried at room temperature under reduced pressure for 1 hour to obtain a vinyl copolymer for the non-woven fabric.
  • a composite for capturing microorganisms having a coalescence rate of about 1.0% by weight was prepared.
  • Example 6 (41 mg, 0.25 mmo ⁇ ) was reacted under the same conditions as in Example 6 to copolymerize (4-vinylbenzyl chloride / vinylidene chloride) at a molar ratio of 2 Z 3. The obtained compound was obtained. The above molar ratio was confirmed by NMR. Next, 4-vinylbenzyl chloride was quaternized with an equimolar amount of pyridine to obtain a quaternary ammonium salt-containing polymer. A composite for capturing microorganisms was obtained in the same manner as in Example 19, except that the obtained quaternary ammonium salt-containing polymer was used.
  • This complex for capturing microorganisms was immersed in a solution containing activated sludge for 14 hours or 48 hours in the same manner as in Example 19, and the activated sludge tank was reciprocated at 50 rpm. .
  • the cells adhering to the above-mentioned complex for capturing microorganisms are stained with methylene blue, and the absorbance is measured.
  • a nonwoven fabric made of polyethylene terephthalate (PET) (fineness: 0.016 decitex) was punched into 2 cm ⁇ to obtain a carrier for adsorbing microorganisms.
  • Escherichia coli was suspended in saline at a concentration of 5 ⁇ 10 8 cells / m 1.
  • the turbid solution was passed through the column at a rate of 45 m 1 / r.
  • Example 22 Without using the quaternary ammonium salt-containing polymer of the present invention, only the PET nonwoven fabric used in Example 21 was filled in a column, and Escherichia coli (Escherichia Coli) was added to physiological saline. Eight suspensions having a concentration of Zm 1 were passed through a column at a rate of .45 m 1 / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time to determine the eradication rate. The results are shown in Table 12.
  • Example 22 Example 22
  • Escherichia coli was suspended in physiological saline at a concentration of 5 ⁇ 10 8 cells / m 1. The solution is passed through the column at a rate of 45 m 1 / r, and the viable cell count in the filtrate is determined. Measured over time. The results are shown in Table 12.
  • Example 2 After stacking two 2 cm-diameter complex for microbial capture obtained in the same manner as in a column of 2 cm in diameter on a column of 2 cm in diameter, Staphylococcus aureus (Staphylococcus aureus) was added to physiological saline. The liquid suspended at a concentration of 3 ⁇ 10 8 Zm 1 was passed through the column at a rate of 60 m 1 / hr. The number of viable bacteria in the filtrate obtained through the passage was measured over time, and the eradication rate was determined. Table 13 shows the results.
  • Staphylococcus aureus Staphylococcus aureus
  • Example 2 After 2 layers of 2 cm ⁇ of the microorganism-capturing complex obtained in the same manner as in Example 1 were packed in a column having an inner diameter of 2 cm by three layers, Pseudomonas aerialeginosa (Ps eudomonas
  • aeruginosa was suspended in physiological saline to a concentration of 6 ⁇ 10 8 particles / m 1 and passed through the column at a rate of 30 ml / hr. The number of viable bacteria in the filtrate obtained by passing the solution was measured over time, and the eradication rate was determined. Table 13 shows the results.
  • a PET nonwoven fabric similar to that used in Example 21 was punched out into a size of 2 cm ⁇ i) as in Example 25, and this was packed into a column having an inner diameter of 2 cm in a stack of 32 pieces. After that, a suspension of Ml 3 pacteriophage at a concentration of 5 x 10 6 particles Zml in physiological saline was passed through the column at a flow rate of 40 ml / hr. The number of particles in the obtained filtrate was measured over time, and the bacteria removal rate was determined. The results are shown in Table 14.
  • Table 14 shows that the complex for capturing microorganisms using the microorganism capturing agent of the present invention works more effectively on microscopic viruses than bacterial cells.
  • Example 21 By a method similar to that of Example 21, a compound in which 4-vinylbenzyl chloride and styrene were copolymerized in a molar ratio of 1: 1 was obtained. Next, 4-vinylbenzyl chloride was quaternized with an equimolar amount of pyridine to obtain a desired quaternary ammonium salt-containing polymer.
  • PET polyethylene terephthalate
  • a nonwoven fabric made of 0. 16 decitex) was punched into 2 cm ⁇ to obtain a carrier for adsorbing microorganisms.
  • the PET non-woven fabric was impregnated with a THF solution (10 mg / ml) in which the quaternary ammonium salt-containing polymer was dissolved for 30 seconds, and then dried at room temperature under reduced pressure for 1 hour to obtain a vinyl copolymer for the non-woven fabric.
  • a complex for capturing microorganisms having a coalescence rate of about 1.0% by mass was obtained.
  • the microorganism scavenger of the present invention (quaternary ammonium salt-containing polymer) only the PET nonwoven fabric used in Example 21 was immersed in a liquid containing active sludge for 14 hours or 48 hours. Then, the activated sludge tank was shaken back and forth at a speed of 50 rpm. The cells attached to the above-described complex for capturing microorganisms were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of the attached cells. Table 16 shows the results.
  • Example 2 9 By a method similar to that in Example 22, a compound copolymerized at a molar ratio of (4-Bielbenzyl chloride Z styrene) of 2 Z 3 was obtained. Next, 4-vinylbenzyl chloride was quaternized with an equimolar amount of pyridine to obtain a desired quaternary ammonium salt-containing polymer. Thus, a complex for capturing microorganisms was obtained.
  • the complex for capturing microorganisms was immersed in a liquid containing activated sludge for 14 hours or 48 hours in the same manner as in Example 28, and the activated sludge tank was reciprocated at a speed of 50 rpm.
  • the cells attached to the above-described complex for capturing microorganisms were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of the attached cells. The results are shown in Table 16.
  • the PET non-woven fabric is impregnated with a THF solution (10 mg / ml) in which the above quaternary ammonium salt-containing polymer is dissolved for 30 seconds, and then dried at room temperature under reduced pressure for 1 hour to obtain a vinyl copolymer for the non-woven fabric.
  • a complex for capturing microorganisms having a coalescence rate of about 1.0% by mass was obtained.
  • the microorganism capturing complex was immersed in a liquid containing denitrifying bacteria for 14 hours or 48 hours, and the denitrifying bacteria tank was shaken back and forth at a speed of 50 rpm.
  • the cells adhered to the above-described complex for capturing microorganisms were stained with methylene blue, and the absorbance (660 nm) was measured over time to determine the amount of the adhered cells. The results are shown in Table 17.
  • This complex for capturing microorganisms was immersed in a denitrifying bacteria-containing solution for 14 hours or 48 hours in the same manner as in Example 30. Reciprocal shaking was performed at a speed of 50 r; pm. The cells adhering to the above complex for capturing microorganisms are stained with methylene blue, and the absorbance (6
  • Example 30 Without using the microorganism-capturing agent of the present invention, only the PET nonwoven fabric used in Example 30 was immersed in a denitrifying bacteria-containing solution for 14 hours or 48 hours, and the denitrifying bacteria tank was rotated at 50 rpm.
  • the results are shown in Table 17.
  • the amount of bacterial cells attached is proportional to the absorbance of the methylelene, and the higher the value of the absorbance (660 nm), the greater the amount of bacterial cells attached is determined.
  • the microorganism-trapping complex using the PET nonwoven fabric to which the microorganism-trapping agents of Examples 30 and 31 were attached was more effective than the comparative example 13 in denitrifying bacteria.
  • the composite for capturing microorganisms of Example 30 to which the microorganism capturing agent of the present invention is attached is superior to the composite for capturing microorganisms of Example 31 to which the microorganism capturing agent of Example 31 is attached. It can be seen that the ability to capture denitrifying bacteria is excellent.
  • Comparative Example 13 in which no microorganism-capturing agent was attached had a weaker ability to capture bacteria. Table 17
  • the quaternary ammonium salt-containing polymer obtained in Example 20 was melt-extruded from a spinneret at an extrusion temperature of 180 ° C by a single screw extruder using a single screw extruder, and quenched by a water cooler.
  • the fiber was drawn four times by a temperature difference nozzle to obtain a fiber consisting of 10 single yarns having a circular cross section of about 100 / m in diameter. These fibers were bundled into 50 bundles each having a length of 50 cm to obtain a fiber bundle for capturing microorganisms.
  • the obtained fiber bundle for capturing microorganisms was immersed in a liquid containing activated sludge bacteria, and the activated sludge tank was reciprocated at a speed of 50 rpm. After a lapse of 68 hours, the fiber bundle for capturing microorganisms was dried at 105 ° C. for 3 hours under normal pressure, and the dry weight of the amount of cells attached to the fiber bundle for capturing microorganisms was measured.
  • the amount of adhered cells on the fiber bundle for capturing microorganisms was calculated as the amount of adhered cells per unit fiber weight of the fiber bundle for capturing microorganisms.
  • the evaluation was based on the amount of cells adsorbed when the amount of cells attached to the comparative example was 100%. The results are shown in Table 18.
  • melt-spinning was performed in the same manner as in Example 32 above, and the diameter of the circular section was about 10 mm. 0 Thus, a fiber composed of 10 m single yarns was obtained.
  • the fibrous mass was measured using the same method as in Example 32, using this fiber as a fifty cm long and fifty fifty rods.
  • the amount of cells attached to the fiber bundle for capturing microorganisms was calculated as the amount of cells attached per unit fiber weight of the fiber bundle for capturing microorganisms.
  • the evaluation was based on the amount of adsorbed cells when the amount of cells attached to the comparative example was 100%. The results are shown in Table 18.
  • Example 3 3
  • the fiber obtained in Example 32 was bundled into 50 bundles of 50 cm in length and immersed in a denitrifying bacteria suspension, and the denitrifying bacteria tank was shaken back and forth at a speed of 50 rpm. 6 After the lapse of 8 hours, dry the amount of cells attached to the microbe bundle for microorganism capture under normal pressure at 105 ° C for 3 hours, and dry the amount of bacteria attached to the microbe bundle. The weight was measured.
  • the amount of adhered cells on the fiber bundle for capturing microorganisms was calculated as the amount of adhered cells per unit fiber weight of the bundle of fibers for capturing microorganisms.
  • the evaluation was based on the amount of cells adsorbed when the amount of cells attached to the comparative example was 100%. The results are shown in Table 18.
  • Example 32 As is evident from Table 18, the microorganism-trapping fibers shown in Example 32 exhibited an excellent effect on capturing activated sludge bacteria and denitrifying bacteria. Comparative Example 15
  • Example 33 Using commercially available polyvinylidene chloride (registered trademark, Saran Wrap; manufactured by Asahi Kasei Corporation, Japan), this was melt-spun in the same manner as in Example 32 above to obtain a circular cross section having a diameter of about 100/100. A fiber consisting of 10 single yarns of im was obtained. The fibers were formed into 50 bundles of 50 cm in length, and the amount of adhered cells was measured in the same manner as in Example 33.
  • polyvinylidene chloride registered trademark, Saran Wrap; manufactured by Asahi Kasei Corporation, Japan
  • the amount of adhered cells on the fiber bundle for capturing microorganisms was calculated as the amount of adhered cells per unit fiber weight of the bundle of fibers for capturing microorganisms.
  • the evaluation was based on the amount of cells adsorbed when the amount of cells attached to the comparative example was 100%. The results are shown in Table 18.
  • the microorganism capturing agent of the present invention not only has excellent microorganism capturing ability, but also can maintain such excellent microorganism capturing ability for a long time. It can be used effectively for capture. Furthermore, since the microorganism capturing agent of the present invention is soluble in an organic solvent and / or a water-containing organic solvent, a microorganism capturing agent containing a carrier on which the capturing agent is supported is used using a solution of the microorganism capturing agent. The composite for use can be easily manufactured.
  • the surface area per unit weight of the microorganism-trapping complex that determines the microorganism-trapping ability of the microorganism-trapping complex is appropriately selected.
  • the complex can be set freely, and a complex for capturing microorganisms having a desired ability to capture microorganisms can be obtained.
  • the complex for capturing microorganisms using the microorganism capturing agent of the present invention can be advantageously used as a carrier for holding microorganisms and cells in bioreactors and biosensors.

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  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un agent de piégeage de micro-organismes, qui se caractérise en ce qu'il comprend un composé présentant au moins deux groupes carboxy; un composé benzotriazole; un composé amide; un composé azo insoluble dans l'eau; un sel d'ammonium quaternaire de la formule (1); et au moins un composé sélectionné dans le groupe constitué par des polymères contenant un sel d'ammonium quaternaire et présentant, respectivement, des chaînes polymériques des formules (2) à (5).
PCT/JP2003/001322 2002-02-07 2003-02-07 Agent de piegeage de micro-organismes WO2003066192A1 (fr)

Priority Applications (2)

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JP2003565612A JP4522707B2 (ja) 2002-02-07 2003-02-07 微生物捕捉剤
AU2003207181A AU2003207181A1 (en) 2002-02-07 2003-02-07 Microorganism-trapping agent

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JP2002/30954 2002-02-07
JP2002030954 2002-02-07
JP2002/141158 2002-05-16
JP2002141158 2002-05-16
JP2002/309541 2002-10-24
JP2002309541 2002-10-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9969885B2 (en) 2014-07-31 2018-05-15 Kimberly-Clark Worldwide, Inc. Anti-adherent composition
US10028899B2 (en) 2014-07-31 2018-07-24 Kimberly-Clark Worldwide, Inc. Anti-adherent alcohol-based composition
US10238107B2 (en) 2014-07-31 2019-03-26 Kimberly-Clark Worldwide, Inc. Anti-adherent composition
US11737458B2 (en) 2015-04-01 2023-08-29 Kimberly-Clark Worldwide, Inc. Fibrous substrate for capture of gram negative bacteria
US12037497B2 (en) 2016-01-28 2024-07-16 Kimberly-Clark Worldwide, Inc. Anti-adherent composition against DNA viruses and method of inhibiting the adherence of DNA viruses to a surface

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018123418A1 (fr) * 2016-12-26 2018-07-05 パナソニックＩｐマネジメント株式会社 Milieu de filtre à air

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5260622A (en) * 1975-11-13 1977-05-19 Eastman Kodak Co Photographic element
JPS61112005A (ja) * 1984-11-05 1986-05-30 Nitto Kasei Kk 防汚剤
JPS637785A (ja) * 1986-06-26 1988-01-13 Kyoritsu Yuki Co Ltd 微生物の固定化方法
JPS63160584A (ja) * 1986-12-24 1988-07-04 Kibun Kk 固定化酵素又は固定化微生物の製造方法
JPS6440506A (en) * 1987-08-07 1989-02-10 Agency Ind Science Techn Antimicrobial and microorganism removing high polymer
JPH01257412A (ja) * 1988-04-08 1989-10-13 Nippon Steel Chem Co Ltd 人工粒状培土
JPH02195882A (ja) * 1988-10-18 1990-08-02 Fuji Photo Film Co Ltd 生理活性物質を固定化した膜の製造方法およびそれによつて得られる膜
JPH03754A (ja) * 1989-05-29 1991-01-07 Otsuka Pharmaceut Factory Inc スチレン系重合体及び接着性細胞培養用担体
EP0586268A1 (fr) * 1992-07-06 1994-03-09 Terumo Kabushiki Kaisha Matériau pour l'élimination de substance pathogène et filtre de sang comprenant un tel matériau
EP0602254A1 (fr) * 1992-07-06 1994-06-22 Otsuka Kagaku Kabushiki Kaisha Monomere polymerisable et son polymere; procede de production associe
JPH06335382A (ja) * 1993-03-31 1994-12-06 Iatron Lab Inc 細胞培養基材及び細胞培養方法
JP2000333672A (ja) * 1999-05-26 2000-12-05 Nippon Shokubai Co Ltd 固定化生体触媒の製造方法
WO2001007090A1 (fr) * 1999-07-21 2001-02-01 The Procter & Gamble Company Dispositif de filtration de microorganismes et procede d'elimination des microorganismes de l'eau
JP2001087782A (ja) * 1999-09-27 2001-04-03 Baioseru:Kk 微生物固定化処理用の発泡担体、並びにこれを用いた有機廃水等の廃水及び富栄養化水の処理方法
JP2001213706A (ja) * 2000-01-31 2001-08-07 Japan Organo Co Ltd 固定化殺菌・抗菌剤
JP2002122954A (ja) * 2000-08-08 2002-04-26 Fuji Photo Film Co Ltd 感光性ハロゲン化銀写真乳剤、これを含有するハロゲン化銀写真感光材料および感光性ハロゲン化銀写真乳剤の感度向上方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632824B2 (ja) * 1985-02-27 1994-05-02 三菱樹脂株式会社 微生物保持体
JPS62116612A (ja) * 1985-11-18 1987-05-28 Mitsubishi Petrochem Co Ltd ビニルイミダゾリウム塩基を側鎖に有する線状高分子及びその製造法
JPH025852A (ja) * 1988-06-25 1990-01-10 Nippon Steel Chem Co Ltd 微生物担体
JP3171691B2 (ja) * 1992-08-31 2001-05-28 大塚化学株式会社 共重合体及びその製造方法
JPH0615167A (ja) * 1992-07-06 1994-01-25 Terumo Corp 多孔性分離膜
JPH06264056A (ja) * 1993-03-11 1994-09-20 Kankyo Riyokuka Shigen Kaihatsu Center:Kk 土壌改良剤および微生物担体
JP3539650B2 (ja) * 1995-10-05 2004-07-07 ゴールド興産株式会社 水処理用セラミックス
JP3118604B2 (ja) * 1998-03-10 2000-12-18 日本バイリーン株式会社 微生物吸着樹脂

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5260622A (en) * 1975-11-13 1977-05-19 Eastman Kodak Co Photographic element
JPS61112005A (ja) * 1984-11-05 1986-05-30 Nitto Kasei Kk 防汚剤
JPS637785A (ja) * 1986-06-26 1988-01-13 Kyoritsu Yuki Co Ltd 微生物の固定化方法
JPS63160584A (ja) * 1986-12-24 1988-07-04 Kibun Kk 固定化酵素又は固定化微生物の製造方法
JPS6440506A (en) * 1987-08-07 1989-02-10 Agency Ind Science Techn Antimicrobial and microorganism removing high polymer
JPH01257412A (ja) * 1988-04-08 1989-10-13 Nippon Steel Chem Co Ltd 人工粒状培土
JPH02195882A (ja) * 1988-10-18 1990-08-02 Fuji Photo Film Co Ltd 生理活性物質を固定化した膜の製造方法およびそれによつて得られる膜
JPH03754A (ja) * 1989-05-29 1991-01-07 Otsuka Pharmaceut Factory Inc スチレン系重合体及び接着性細胞培養用担体
EP0586268A1 (fr) * 1992-07-06 1994-03-09 Terumo Kabushiki Kaisha Matériau pour l'élimination de substance pathogène et filtre de sang comprenant un tel matériau
EP0602254A1 (fr) * 1992-07-06 1994-06-22 Otsuka Kagaku Kabushiki Kaisha Monomere polymerisable et son polymere; procede de production associe
JPH06335382A (ja) * 1993-03-31 1994-12-06 Iatron Lab Inc 細胞培養基材及び細胞培養方法
JP2000333672A (ja) * 1999-05-26 2000-12-05 Nippon Shokubai Co Ltd 固定化生体触媒の製造方法
WO2001007090A1 (fr) * 1999-07-21 2001-02-01 The Procter & Gamble Company Dispositif de filtration de microorganismes et procede d'elimination des microorganismes de l'eau
JP2001087782A (ja) * 1999-09-27 2001-04-03 Baioseru:Kk 微生物固定化処理用の発泡担体、並びにこれを用いた有機廃水等の廃水及び富栄養化水の処理方法
JP2001213706A (ja) * 2000-01-31 2001-08-07 Japan Organo Co Ltd 固定化殺菌・抗菌剤
JP2002122954A (ja) * 2000-08-08 2002-04-26 Fuji Photo Film Co Ltd 感光性ハロゲン化銀写真乳剤、これを含有するハロゲン化銀写真感光材料および感光性ハロゲン化銀写真乳剤の感度向上方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9969885B2 (en) 2014-07-31 2018-05-15 Kimberly-Clark Worldwide, Inc. Anti-adherent composition
US10028899B2 (en) 2014-07-31 2018-07-24 Kimberly-Clark Worldwide, Inc. Anti-adherent alcohol-based composition
US10238107B2 (en) 2014-07-31 2019-03-26 Kimberly-Clark Worldwide, Inc. Anti-adherent composition
US10292916B2 (en) 2014-07-31 2019-05-21 Kimberly-Clark Worldwide, Inc. Anti-adherent alcohol-based composition
US11737458B2 (en) 2015-04-01 2023-08-29 Kimberly-Clark Worldwide, Inc. Fibrous substrate for capture of gram negative bacteria
US12037497B2 (en) 2016-01-28 2024-07-16 Kimberly-Clark Worldwide, Inc. Anti-adherent composition against DNA viruses and method of inhibiting the adherence of DNA viruses to a surface

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AU2003207181A1 (en) 2003-09-02
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TW200305586A (en) 2003-11-01
JP4522707B2 (ja) 2010-08-11

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