JP2001213706A - Immobilized bactericidal and antibacterial agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an immobilized bactericidal and antibacterial agent having a significant high density of bactericidal and antibacterial ingredient on the surface without nearly releasing of the ingredient. SOLUTION: The agent has a monomolecular film or bimolecular film composed of amphiphilic chain organic molecules having quaternary ammonium group as a top surface layer. As a method for preparing the agent, for example, a method by supporting the molecules through the ionic, bond with the ion exchange group of an ion exchange resin used as a carrier can be suitably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an immobilized bactericidal / antibacterial agent having a surface having excellent bactericidal / antibacterial properties.

[0002]

2. Description of the Related Art Sterilization / antibacterial is a chemical method in which a germicide such as hypochlorous acid or ozone is applied to an object (object to be treated), or a physical method in which heat, ultraviolet rays, etc. are applied. It is performed by a method or a method combining these.

[0003] In the above-mentioned chemical method, when the object to be treated is a liquid, a disinfectant / antibacterial agent is dissolved in the object to be treated. When the object to be treated is a solid, it is sprayed on the surface thereof, or sterilized / antibacterial. The object to be treated is immersed in a disinfectant / antibacterial solution in which the agent is dissolved. In this case, the disinfectant / antibacterial agent is basically disposable, and requires an amount of the disinfectant / antibacterial agent substantially in proportion to the amount to be treated. In addition, since the disinfectant / antibacterial agent is dissolved or adhered and remains in the object to be treated, while exhibiting a continuous disinfectant / antibacterial effect, it may exhibit toxicity to humans, for example, a halogen-based compound such as hypochlorous acid. Fungicides can produce harmful organics such as trihalomethane when co-existing with organics.

[0004] In order to solve the above-mentioned problems of the disinfectant / antibacterial agent and to facilitate its use, an immobilized disinfectant / antibacterial agent in which the disinfectant / antibacterial agent is immobilized on a solid (carrier, substrate) surface has been developed. Is being developed. Immobilized bactericidal / antibacterial agents include immobilizing bactericidal / antibacterial components on solid surfaces by methods such as physical adsorption or ionic bonding of the bactericidal / antibacterial components to the carrier surface, kneading with the base material, or various types of bactericidal / antibacterial components. Examples include those more firmly immobilized on an organic or inorganic carrier via a covalent bond. Examples of the immobilized sterilizing and antibacterial agents that have been developed so far include those in which a metal having a sterilizing effect such as silver or copper is physically adsorbed to an adsorbent such as activated carbon or zeolite, or the metal is adsorbed. Activated carbon or zeolite powder is further kneaded into a polymer material such as nylon and processed into fibrous form, iodine is immobilized on the surface of an anion exchange group carrier by ionic bonding, polymyxin is converted into agarose Bonded, bactericidal / antibacterial agent with an alkoxysilyl group introduced and hydroxyl group on the carrier surface, etc. bonded by a dealcoholization reaction to immobilize the bactericidal / antibacterial agent by covalent bond, benzyl group, methylene group, ester Bactericidal and antibacterial agents immobilized on the polymer chain by covalent bonds, etc., and then applied or coated on the surface of the article to be treated. The surface of the article to be treated can be mentioned as a fixed sterilizing / antibacterial agent, and these fixed sterilizing / antibacterial agents have already been used as fillers for sterilization of drinking water, etc. Sterilization and antibacterialization of daily necessities such as food containers and packaging, building materials such as wallpaper, toothbrushes, towels, bedding, clothing, kitchen utensils, stationery, and electric appliances, and sterilization and antibacterialization of various equipment at medical sites such as hospitals. [Korean Hiroki,
"Immobilized fungicide", Chemistry and Biology, Vol. 26, No. 12,
834-841 (1988)].

[0005]

However, the above-mentioned immobilized sterilizing / antibacterial agent has the following problems. That is, immobilized sterilization in which the sterilization / antibacterial component is immobilized on a solid surface by a method such as physical adsorption, ionic bonding, and mixing.
In antibacterial agents, there is a slight release of antibacterial and antibacterial agent components, and not only unavoidable aging of sterilization and antibacterial effects,
The toxicity of the released bactericidal and antibacterial components may affect humans. In the immobilized bactericidal / antibacterial agent in which the bactericidal / antibacterial component is more firmly immobilized on various organic or inorganic carriers via a covalent bond, the bactericidal / antibacterial component is physically adsorbed,
Release of the bactericidal / antibacterial agent component is suppressed as compared with the immobilized bactericidal / antibacterial agent immobilized on the solid surface by a method such as ionic bonding or kneading. However, in the immobilized bactericidal / antibacterial agent obtained by immobilizing the bactericidal / antibacterial agent component by the above covalent bond, the bactericidal / antibacterial agent component is supported at a certain distance derived from the structure of the supported solid,
The germicidal and antimicrobial components do not have a densely arranged surface structure at the molecular level. Since the germicidal / antibacterial effect of the immobilized germicidal / antibacterial agent is expressed by the contact between the germicidal / antibacterial agent component and the cells, the germicidal / antibacterial agent is adhered to the surface of the immobilized germicidal / antibacterial agent by contamination. When the amount of the component that can effectively act is reduced, particularly in a system where the number of cells to be sterilized is small, such as in a sterilized water production system such as ultrapure water or in a transfer piping system of the sterilized water. Cannot exert a sufficient bactericidal effect.

That is, an object of the present invention is to provide an immobilized bactericidal / antibacterial agent which hardly releases the bactericidal / antibacterial component and has a remarkably high density of the bactericidal / antibacterial component on the surface.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems of the conventional immobilized bactericidal and antibacterial agents, and as a result, have found that an amphiphilic chain having a quaternary ammonium group has been obtained. If the monolayer or bilayer made of organic molecules is used as the outermost layer, there is almost no release of the bactericidal / antibacterial agent component, and the new immobilized bactericidal / antibacterial agent has a significantly higher density of bactericidal / antibacterial agent components on the surface. The inventors have found that an antibacterial agent can be prepared, and have reached the present invention.

That is, the present invention provides an immobilized bactericidal / antibacterial agent characterized in that a monolayer or a bilayer consisting of amphiphilic chain organic molecules having a quaternary ammonium group is the outermost layer. Is what you do.

According to the present invention, a monomolecular film or a bimolecular film formed by arranging amphiphilic chain organic molecules having a quaternary ammonium group in water is used as the outermost layer, so that immobilized sterilization and sterilization can be achieved. The antimicrobial agent can have a dramatically higher surface sterilization / antimicrobial agent component density. The immobilized bactericidal / antibacterial agent of the present invention has almost no release of the bactericidal / antibacterial agent component, so there is almost no possibility that the germicidal / antibacterial effect deteriorates with time and the toxicity of the released bactericidal / antibacterial agent component extends to humans. In addition, since the density of the germicidal / antibacterial agent component on the surface is extremely high, the bacterium to be sterilized, for example, in a sterilized water production system such as ultrapure water or in a transfer piping system of the sterilized water. Even in a system with a small number of bodies, a sufficient bactericidal effect can be exhibited.

The amphiphilic substance is a group of compounds consisting of a lyophobic group having a weak interaction with a solvent molecule such as a water molecule and an amphiphilic group having a strong interaction. , Long-chain carboxylic acids, soaps, synthetic detergents, dyes,
Examples include phospholipids. Some amphiphilic substances form a monomolecular film or a bimolecular film by self-assembly when dispersed in an aqueous solvent such as water. An amphiphilic substance forming a monomolecular film or a bimolecular film is generally composed of organic molecules whose molecular shape is a chain, for example, as shown below, a double-stranded amphiphilic compound, a single-stranded Type amphiphilic compounds, multi-chain type amphiphilic compounds, fluorocarbon chain type amphiphilic compounds, amphiphilic chain compounds having hydrophilic groups at both molecular ends, and composite substances thereof.

Examples of the double-stranded amphiphilic compound include compounds represented by formulas (1) to (13), and among these, compounds (1) to (6) Have a quaternary ammonium group, and can be used as an amphiphilic chain organic molecule having a quaternary ammonium group in the present invention. In the formula of “Chemical formula 7,” “M” represents a metal element capable of forming a chelate with N atoms such as Fe and Cu. In the following chemical formulas, * represents an asymmetric carbon atom, and n,
m and x represent a positive integer suitable for making the substance of each formula amphiphilic.

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

Examples of the single-chain type amphiphilic compound include compounds represented by the formulas (Chemical Formula 14) to (Chemical Formula 19). Have a quaternary ammonium group, and can be used as an amphiphilic chain organic molecule having a quaternary ammonium group in the present invention.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

Examples of the polychain amphiphilic compound include:
Compounds represented by the formulas “Chemical Formula 20” to “Chemical Formula 22” can be mentioned, which have a quaternary ammonium group, and have an amphiphilic property having a quaternary ammonium group in the present invention. It can be used also as a chain organic molecule.

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

Examples of the fluorocarbon chain type amphiphilic compound include compounds represented by formulas (Formula 23) to (Formula 28), which have a quaternary ammonium group. In the present invention, it can be used as an amphiphilic chain organic molecule having a quaternary ammonium group.

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

Examples of the amphiphilic compound having a hydrophilic group at both ends of the molecule include compounds represented by the formulas (Chemical Formula 29) to (Chemical Formula 36). -The compounds represented by the formulas (Formula 31) and (Formula 35) have a quaternary ammonium group, and in the present invention, they may be used as amphiphilic chain organic molecules having a quaternary ammonium group. It can be used.

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

As the composite amphiphile, for example,
Examples of the substances represented by the formulas (Chemical Formula 37) and (Chemical Formula 38) include those having a quaternary ammonium group, and in the present invention, amphiphilic having a quaternary ammonium group. It can be used also as a chain organic molecule. Note that, in the formula of “Chemical Formula 38”, dots arranged in the vertical direction indicate that two kinds of molecules are alternately arranged by hydrogen bonds, and between N and H and between O and H. Form a hydrogen bond.

[0053]

Embedded image

[0054]

Embedded image

Among the above-mentioned amphiphilic substances, those not mentioned as those which can be used as amphiphilic chain organic molecules in the present invention have strong interaction with solvent molecules such as water. The amphiphilic group is not a quaternary ammonium group. Further, when a plurality of kinds of amphiphilic chain organic molecules as exemplified above are mixed and used, a monomolecular film or a bimolecular film can be formed, and a desirable sterilizing / antibacterial activity according to the application is obtained. In the present invention, a plurality of such amphiphilic chain organic molecules can be used in combination, as long as a bactericidal / antibacterial agent having a quaternary ammonium group can be used. In addition to the chain organic molecules, amphiphilic chain organic molecules having no quaternary ammonium group may be mixed and used. When an amphiphilic chain organic molecule having no quaternary ammonium group is used in addition to the amphiphilic chain organic molecule having a quaternary ammonium group, the immobilized sterilizing / antibacterial agent is used. The arrangement of the hydrophobic portion of the amphiphilic chain organic molecule having a quaternary ammonium group present in the outermost layer due to the hydrophobic interaction between the hydrophobic portions becomes sparse or indirect. There is no doubt that a monomolecular film or a bimolecular film comprising an amphiphilic chain organic molecule having a quaternary ammonium group is formed.

When an amphiphilic chain organic molecule forms a monomolecular film or a bimolecular film in water, the surface has a structure in which hydrophilic groups are arranged at a high density, and the inside of the film has a hydrophobic portion having a hydrophobic portion. It takes a structure arranged by sexual interaction. At this time, even when the hydrophilic group is an ion dissociable functional group such as a quaternary ammonium group, a phosphoric acid group, or a sulfonic acid group, the counter ion sometimes acts to cancel the charge. Therefore, the hydrophobic interaction overcomes the charge repulsion between ion-dissociative functional groups, enabling high-density arrangement of ion-dissociative hydrophilic groups, and in some cases, the two-dimensional close packing of ion-dissociative hydrophilic groups. It is considered that high-density arrangement with high regularity is possible.

According to the present invention, an amphiphilic substance forming at least one quaternary ammonium group among the above-mentioned monomolecular or bimolecular film-forming amphiphilic substances is replaced with an ion-exchange resin,
Synthetic organic adsorbents, organic substances such as organic fibers or inorganic substances such as glass or metal, or by supporting them on a carrier such as a composite thereof, or further, after supporting the monomolecular film or the bimolecular film In addition to the hydrophobic interaction, the amphiphilic chain organic molecules constituting the monomolecular film or the bimolecular film are bonded by a hydrogen bond and / or a covalent bond, so that the bactericidal / antibacterial component can be obtained. Prevent release of a certain quaternary ammonium group and prepare immobilized disinfectant / antibacterial agent with a remarkably high surface disinfectant / antibacterial component density by using a monolayer or bilayer as the outermost layer. is there. The immobilized bactericidal / antibacterial agent of the present invention thus obtained also has physical strength enough to withstand industrial use, for example, in a system for producing sterilized water such as ultrapure water or a transfer pipe for the sterilized water. A sufficient bactericidal effect can be exhibited even in a system having a small number of cells to be sterilized, such as in a system.

In the present invention, a monomolecular film or a bimolecular compound may be mixed with an amphiphilic chain organic molecule having a quaternary ammonium group or an amphiphilic chain organic molecule having a quaternary ammonium group. Other amphiphilic chain organic molecules capable of forming a film include, but are not limited to, any as long as they self-assemble in water to form a monomolecular film or a bimolecular film. An azobenzene compound having high density and regularity of hydrophobic interaction, particularly as shown in the formula of Chemical formula 39, wherein n = 6 or more and m = 8 or more, n = 8 to 16 and m = 10 To 16 are more preferable, and n = 8 and m = 10 are particularly preferable].

[0059]

Embedded image

In general, an amphipathic chain having a hydrophilic group at both molecular ends forms a monomolecular film, and an amphipathic chain having a hydrophilic group at one end of the molecule forms a bilayer. In the present invention, whether the film formed by the amphiphilic chain organic molecule is a monolayer or a bilayer, the target surface sterilization / immobilized sterilization / antibacterial having a high antimicrobial agent component density is desired. Agent can be obtained.

The material for supporting the monomolecular film or the bimolecular film can be selected from materials and shapes depending on the purpose, and is not limited to a specific carrier. Alternatively, an organic substance such as a synthetic organic adsorbent or an organic fiber, an inorganic substance such as glass or metal, or a composite thereof can be used. In addition, when a method for forming a monomolecular film or a bimolecular film utilizing a radical reaction described below is used, it is also possible to use inorganic substances or organic polymer compounds of a wide variety of types in which an organic group is introduced or modified on the surface. it can.

[0062]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described focusing on a method for producing an immobilized sterilizing / antibacterial agent of the present invention, but the present invention is not limited thereto.

One method for supporting a monomolecular film or a bimolecular film on a carrier as described above is to coat the surface of the carrier with a thin film of a polymer electrolyte and then support the monomolecular film or the bimolecular film by ionic bonding. There is a way to make it happen. That is, on the surface of the carrier, for example, a thin film of a polymer electrolyte such as polyethyleneimine or polystyrenesulfonic acid is coated alone or alternately, and then the amphiphilic chain organic molecules are dispersed in water in which the coated carrier is immersed. A monolayer or bilayer is supported on the coated carrier by ionic bonding to obtain an immobilized sterilizing / antibacterial agent.

On the other hand, when the carrier itself has an ion exchange group, it is not always necessary to coat the carrier with the above-mentioned polymer electrolyte thin film. That is, for example, an amphiphilic chain organic molecule having a quaternary ammonium group is dispersed in water in which a carrier having a cation exchange group is immersed, and a monolayer or a bilayer is formed on the carrier by ionic bonding. Carry it,
A method for obtaining an immobilized sterilizing / antibacterial agent can also be adopted. Of course, a carrier having an anion exchange group is coated with a thin film of a polymer electrolyte having an anionic dissociation group such as polystyrene sulfonic acid, and then dispersed in water to form an amphiphilic chain organic compound having a quaternary ammonium group. A method in which a monomolecular film or a bimolecular film is supported by ionic bonding with a molecule to obtain an immobilized bactericidal / antibacterial agent can also be adopted. When the amphiphilic chain organic molecule having a quaternary ammonium group further has an anionic dissociating group, a monomolecular film or a bimolecular film is formed on the carrier by ionic bonding using the anionic dissociating group. A method in which a molecular membrane is supported to obtain an immobilized sterilizing / antibacterial agent can also be adopted.
Some examples of such carriers include various ion-exchange resins such as spherical or particulate ion-exchange resin particles, ion-exchange membranes, and ion-exchange fibers.

It is preferable to use ion exchange resins as a carrier for supporting a monomolecular film or a bimolecular film. In this case, the monomolecular film or the bimolecular film is supported on the ion exchange resin by an ionic bond formed between the ion dissociable functional group of the monomolecular film and the ion exchange resin of the ion exchange resin serving as a carrier. . Generally, the surface of an ion exchange resin does not have a structure in which ion exchange groups are densely arranged at a molecular level. For this reason, all the ion dissociable functional groups on the surface of the monomolecular film or the bimolecular film on the side bonded to the ion exchange resin do not participate in ionic bonding. Some of the ion-dissociable functional groups of the monolayer or bilayer form an anchor by forming an ionic bond with the ion-exchange group of the ion-exchange resin serving as a carrier, and the hydrophobic portion of the amphiphilic chain organic molecule is formed. Are arranged by hydrophobic interaction, so that a monolayer or bilayer is formed on the surface of the ion-exchange resin serving as a carrier, and an immobilized sterilizing / antibacterial agent having physical strength that can withstand practical use can be obtained. . As an ion exchange resin serving as a carrier, a resin having an ion exchange group having a polarity opposite to the ion dissociable functional group of a monolayer or bilayer of an amphipathic chain organic molecule to be ion-bonded is used. To be elected.
That is, ion-dissociative functional group of the amphiphilic chain organic molecules to try to form an ion-exchange group and an ion binding ion-exchange resin is a sulfonic acid group ^{_{(R-SO 3 - H +}} ), a carboxylic acid group (R —COO ⁻ H ⁺ ), a phosphonic acid group [RP
(O) (O ⁻ H ⁺ ) ₂ ], a phosphinic acid group [R-PH
(O) (O ⁻ H ⁺ )], an arsenite group (R-OAsO)
^- H ^+), phenoxide group ^{_{(R-C 6 H 4 O}} - if ^{H +)} an anionic dissociative group such as ion-exchange resin as a carrier used is an anion exchange resin, also, the ion-exchange The ion-dissociable functional group of the amphiphilic chain organic molecule which is to form an ionic bond with the ion exchange group of the resin is a quaternary ammonium group (RN ⁺ R ₁ R ₂ R ₃ ) or a tertiary sulfonium. group ^{(R-S + R 1 R} 2), when a cationic dissociative group such as a primary to tertiary amino groups as ion-exchange resin as a carrier a cation exchange resin is used. The ion exchange resin serving as a carrier may be any resin having an ion exchange group having a polarity opposite to the ion dissociable functional group of the amphiphilic chain organic molecule that is to form an ionic bond. There is no particular limitation.

In the method using an ion exchange resin as a carrier, the shape is selected from spherical, particulate, flake, membrane, and fibrous shapes according to the purpose, and the brand is appropriately selected according to the purpose. Can be. As an anion exchange resin,
For example, Amberlite IRA400, IRA402BL, IRA900 and the like manufactured by Rohm and Haas Co., and as cation exchange resins, for example, Amberlite IR120B and R1400 manufactured by Rohm and Haas Co.
R124, 200CT and the like can be suitably used.

When an organic substance such as a synthetic organic adsorbent or an organic fiber, an inorganic substance such as glass or metal, or a composite thereof is used as a carrier, a monolayer or bilayer supporting a monolayer or a bilayer can be used. Is a method in which an amphiphilic chain organic molecule is covalently bonded to the surface of a carrier. For example, a weakly basic ion-exchange resin having a primary amino group (a kind of synthetic organic adsorbent) is reacted with an amphiphilic chain organic molecule having a carboxyl group, and both are reacted via an amide group formed. After covalently bonding and modifying the surface of the carrier with amphiphilic chain organic molecules, the amphiphilic chain organic molecule having at least one quaternary ammonium group is immersed in water in which the surface-modified carrier is immersed. A method of dispersing and forming a monomolecular film or a bimolecular film on a carrier, or a method of converting a weakly basic ion exchange resin having a tertiary amino group and an amphiphilic chain organic molecule having a halogen atom into a quaternary After the support surface is modified with an amphiphilic chain organic molecule by a covalent bond by an oxidization reaction, the amphiphilic chain having at least one quaternary ammonium group in water in which the surface-modified carrier is immersed. Dispersed organic molecules Method of forming & carrying a monomolecular film or a bilayer film and the like onto the carrier Te.

As still another method for supporting a monomolecular film or a bimolecular film on a carrier, the surface of an organic material such as a synthetic organic adsorbent or organic fiber serving as a carrier, or an inorganic material such as glass or metal can be used. After coating with gold and / or silver, an amphiphilic chain organic molecule containing a sulfur atom is dispersed in water in which the coated carrier is immersed to form a bond between gold and / or silver and sulfur on the coated carrier. There is a method of supporting a monomolecular film or a bimolecular film by the method [for the bond of gold and / or silver and sulfur,
For example, Kuniyoshi Aramaki, "Prevention of Copper Corrosion by Self-Assembled Film", Surface, Vol. 36, no. 5 (1998), and Toshihiro Kondo, Kohei Uozaki, "Utilization of Gold-Sulfur Bond:
Self-Assembled Monolayer (SAM) ", Chemistry and Industry, No. 52
Vol. 7, No. 7 (1999)]. In this method, as a carrier for supporting a monomolecular film or a bimolecular film, its material, shape and the like can be selected according to the purpose, and it is not limited to a specific carrier. 0.
Spherical glass beads having a size of 2 to 1 mm are inexpensive and suitable for packing the immobilized sterilizing / antibacterial agent to be manufactured into the column. The method of coating such a carrier with gold and / or silver is not particularly limited as long as the immobilized bactericidal / antibacterial agent to be manufactured has physical strength enough to withstand practical use. An evaporation method or the like can be used. Amphiphilic chain organic molecules containing a sulfur atom to be supported on a carrier coated with gold and / or silver,
There is no particular limitation as long as the sulfur atom can easily form a bond with gold and / or silver. For example, bis (11-trimethylammonium undecaca) represented by the following formula Noylaminoethyl) disulfide halogen salt and the like can be suitably used. In addition,
Platinum, copper, and the like can be used as the coating material, but the above-mentioned gold and / or silver are preferable in terms of cost, oxidation resistance, and the like.

[0069]

Embedded image

The carrier is irradiated with radiation such as γ-rays or accelerated electron beams to generate radicals, and at least one
A method of introducing an amphiphilic chain organic molecule having a quaternary ammonium group onto the surface of the carrier by using a radical reaction can also be adopted (Japanese Patent Application No. 2000-23407). In this case, as a carrier that can be used, for example, metal oxides such as silica, alumina, titania, zirconia, and zeolite whose surface is modified with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. And, clay minerals such as mica, talc, montmorillonite, and activated carbon, surface-modified inorganic compounds having an organic group introduced on the surface thereof, such as inorganic carbon materials such as carbon fiber, and the like,
Various organic polymers such as olefin homopolymers such as polyethylene and polypropylene, copolymers between olefins, and copolymers of olefins with other polymerizable monomers. Molecular compounds,
Examples of the amphiphilic chain organic molecule that can be used include, for example, a thiol group, a disulfide group, a dithiocarbamate group, a halogenated carbon group (at least one halogen-carbon bond) as a functional group having reactivity with a radical. ), Nitroxyl group, ethylene group, styryl group,
Groups containing unsaturated double bonds such as α, β-unsaturated carbonyl groups, groups containing conjugated double bonds such as polyene such as butadiene, and groups containing unsaturated triple bonds such as acetylene and diacetylene Specific examples thereof include amphiphilic substances having a fluorocarbon group represented by the formulas “Chemical Formula 23” to “Chemical Formula 28” and “Chemical Formula 36” and the formulas of “Chemical Formula 40”. And amphiphilic substances containing a disulfide group such as a halogen salt of bis- (11-trimethylammonioundecanoylaminoethyl) disulfide.

In order to further improve the physical strength of the monolayer or bilayer supported on the carrier, the amphiphilic chain organic molecules constituting the monolayer or bilayer are separated from each other by the hydrophobic part. In addition to the interaction, it is preferred that they are further bonded by hydrogen bonds and / or covalent bonds.

Examples of the group or bond capable of forming a hydrogen bond by being introduced into an amphiphilic chain organic molecule include an amide group, a urea bond, and a urethane bond. The halogen salt of bis (11-trimethylammonioundecanoylaminoethyl) disulfide is an example in which an amide group forms a hydrogen bond between molecules and improves the physical strength of the immobilized sterilizing / antibacterial agent.

On the other hand, in order to form a covalent bond, a group containing an unsaturated double bond such as an ethylene group, a styryl group, an α, β-unsaturated carbonyl group, or a conjugated double bond such as a polyene such as butadiene is used. A group containing at least one unsaturated triple bond such as acetylene, diacetylene or the like is introduced into a part of the amphiphilic chain organic molecule, and heating and / or irradiation of light or radiation and / or Addition of a radical initiator is performed to form a covalent bond.

The site for introducing a functional group for forming these bonds is not particularly limited, but in order to further increase the physical strength of the monolayer or bilayer, a site as close as possible to the site for bonding to the carrier is used. Preferably it is introduced.

[0075]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited thereto. In addition,
L represents liter.

Example 1 In this example, p- (10-dimethylhydroxyethylammoniodecyloxy) -p 'was added to the surface of the ion-exchange resin particles.
-This is an example in which water was sterilized using an immobilized sterilizing / antibacterial agent carrying a bilayer of octyloxyazobenzene via an ionic bond.

[1] Preparation of bromine salt of p- (10-dimethylhydroxyethylammoniodecyloxy) -p'-octyloxyazobenzene The above compound is prepared in the following four steps 1) to 4). Was.

1) Production of p-octyloxyaniline hydrochloride Potassium hydroxide (purity: 85%) was placed in a 100 L reactor.
After adding 50 mol of ethanol and 50 L of ethanol and dissolving uniformly, 27 mol of p-acetylaminophenol and 27 mol of octyl bromide were added, and the mixture was reacted with heating under reflux for 8 hours. After cooling to room temperature, the precipitated potassium bromide was filtered off.
15 L of 5% concentrated hydrochloric acid was added, and the mixture was reacted for 9 hours under reflux. The resulting solution was concentrated and cooled to room temperature, and the resulting crystals were filtered off and recrystallized from ethyl acetate. The yield is
53%.

2) Production of p- (octyloxy) -p'-hydroxyazobenzene In a 300 L reactor, 14 mol of p-octyloxyaniline hydrochloride, 50 L of acetone, 50 L of water, 35% concentrated hydrochloric acid 3
After 0 mol was added and uniformly dissolved, the mixture was cooled to 5 ° C. or lower. 15 mol of sodium nitrite and 10 L of water are added to this solution.
Aqueous sodium nitrite solution was gradually added. Separately, 15 mol of potassium hydroxide (purity: 85%) and 15 mol of potassium carbonate were made into an aqueous solution, 15 mol of phenol was dissolved, cooled to 5 ° C. or lower, and gradually added to the previously obtained solution. After stirring at 10 ° C. or lower for 4 hours, the pH was adjusted to 3 with concentrated hydrochloric acid, the resulting solid was separated by filtration, washed sufficiently with water, and recrystallized from benzene. The yield was 70%.

3) p- (10-bromodecyloxy)-
Production of p'-octyloxyazobenzene Potassium hydroxide (85% purity) in a 100 L reactor
Then, 40 mol of ethanol and ethanol were added and uniformly dissolved, and then 9 mol of p- (octyloxy) -p'-hydroxyazobenzene and 46 mol of dibromodecane were added, and the mixture was reacted under heating and reflux for 6 hours. After cooling to room temperature, the precipitated solid was separated by filtration, washed with hexane and then with water. In order to purify the obtained solid, it was recrystallized from a benzene-ethanol (1: 1 by volume) mixed solvent. The yield was 70%.

4) Preparation of a bromine salt of p- (10-dimethylhydroxyethylammoniodecyloxy) -p'-octyloxyazobenzene 550 mmol of p- (10-bromodecyloxy) -p'-octyloxyazobenzene and N , N-dimethylethanolamine was heated and refluxed for 70 hours in a toluene solvent to cause a reaction. After cooling to room temperature, the precipitated solid was separated by filtration, and benzene-ethanol (volume ratio 1: 1) was used.
1) Recrystallization from a mixed solvent. The yield was 70%.

[2] Production of immobilized bactericidal / antibacterial agent 200 mmol of the bromine salt of p- (10-dimethylhydroxyethylammoniodecyloxy) -p'-octyloxyazobenzene prepared as described above was added to 20 L of water. 10 g (dry weight) of Amberlite IR120B, which is a strongly acidic cation exchange resin, is immersed in this dispersion for 20 minutes, filtered, washed with water, and p- (10-dimethylhydroxyethylammoniodecyloxy) -P '
Approximately 12 ml (wet volume) of an immobilized bactericidal / antibacterial agent having a bilayer made of octyloxyazobenzene as the outermost layer was obtained.

The bactericidal effect of water was confirmed using the immobilized bactericidal / antibacterial agent obtained as described above. The column was filled with the immobilized sterilizing / antibacterial agent (12 ml) and the number of viable bacteria was 10 / m
When 1 l of ion-exchanged water was passed at SV = 30, treated water with 0 viable bacteria / ml was obtained. Furthermore, the above-mentioned immobilized sterilization
When industrial water having a viable cell count of 8.6 × 10 ³ / ml was passed through the antibacterial agent packed column at SV = 30, the viable cell count was 5 / m
1 treated water was obtained.

According to this example, the immobilized bactericidal / antibacterial agent of the present invention has a sufficient bactericidal effect even in a system having a relatively large number of cells to be sterilized or in a system having a small number of cells. It was shown to work.

[0085]

According to the present invention, the release of a bactericidal / antibacterial agent component is achieved by making the monolayer or bilayer composed of amphiphilic chain organic molecules having a quaternary ammonium group the outermost layer. Because there is almost no, there is almost no possibility that the germicidal / antibacterial effect of the aging of the bactericidal / antibacterial effect and the toxicity of the released bactericidal / antibacterial agent component reach humans, and the density of the bactericidal / antibacterial agent component on the surface is dramatically higher. For example, in a sterilized water production system such as ultrapure water or in a transfer piping system for the sterilized water, for example, an immobilized sterilization method capable of exhibiting a sufficient sterilization effect even in a system having a small number of cells to be sterilized. An antimicrobial agent can be provided.

Further, examples of uses of the immobilized sterilizing / antibacterial agent of the present invention include use as a filler for sterilization of drinking water, building materials such as food containers and packaging materials, wallpaper, and the like.
Examples include toothbrushes, towels, bedding, clothing, kitchen utensils, stationery, daily necessities such as electric appliances, sterilization and antibacterialization of various appliances at medical sites such as hospitals, and the like.

Claims (1)

[Claims] 1. An immobilized bactericidal / antibacterial agent comprising a monolayer or a bilayer consisting of amphiphilic chain organic molecules having a quaternary ammonium group as the outermost layer.