WO2009099055A1

WO2009099055A1 - Antibacterial hyperbranched polymer

Info

Publication number: WO2009099055A1
Application number: PCT/JP2009/051770
Authority: WO
Inventors: Takehisa Iwama
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2008-02-07
Filing date: 2009-02-03
Publication date: 2009-08-13
Also published as: JPWO2009099055A1; JP5477573B2

Abstract

Disclosed is a polymer material having excellent processability and excellent antibacterial or bactericidal effect. Specifically disclosed is an antibacterial or bactericidal agent which is composed of a hyperbranched polymer containing a quaternary ammonium salt represented by Formula (1). [In Formula (1), R1 represents a hydrogen atom or a methyl group; R2, R3 and R4 independently represent a linear, branched or cyclic alkyl group having 1-20 carbon atoms; A1 represents a structure represented by Formula (2); and n represents the number of repeating units which is an integer of 2-100,000.] [In Formula (2), A2 represents a linear, branched or cyclic alkylene group having 1-30 carbon atoms; and Y1, Y2, Y3 or Y4 represents a hydrogen atom.]

Description

Antibacterial hyperbranched polymer

The present invention relates to an antibacterial hyperbranched polymer, and more specifically, to an antibacterial or bactericidal agent comprising a hyperbranched polymer having a cationic functional group.

Recently, the awareness and orientation of sending a hygienic lifestyle in a clean environment has increased, and antibacterial agents have been used in various fields. Many products that have antibacterial functions have been developed so far, such as storage containers for food, drinks, cosmetics, toothbrushes, stationery, home appliances, bedding, and other daily necessities and building materials. Has been applied in various fields that require prevention of bacterial contamination in industry and the environment. However, antibacterial goods with unclear antibacterial effects have become a social problem, and materials with clear antibacterial effects are required. Furthermore, the use of antibacterial goods made from polymer antibacterial materials that are easy to process provides a hygienic and comfortable living environment, and therefore antibacterial polymer materials with excellent processability are required.

Organic antibacterial agents exhibiting antibacterial properties include quaternary ammonium salts, pyridinium salts, phosphonium salts, pyridine compounds, organic halogen compounds, thiazoline compounds, phenols, imidazolium salts, chlorophenol compounds, pyridine thiol oxide salts, nitro groups Cationic compounds such as morpholine compounds and triazine chloride compounds are known. These cationic compounds are thought to kill bacteria by moving the cell wall and cell membranes through electrostatic interactions between the anion and the cation.

As an antibacterial polymer in which an antibacterial functional molecule is bonded to a polymer, polystyrene having a quaternary ammonium salt bonded (Patent Document 1: Japanese Patent Laid-Open No. 61-246205; Patent Document 2: Japanese Patent Laid-Open No. 2003-55108). And polyacrylates to which quaternary ammonium salts are bonded (Patent Document 3: JP-A-6-9725) have been reported.
These polymers are all linear polymers, and the solubility in solvents and the compatibility with other polymers may be insufficient.
Therefore, problems such as peeling from the fixed base material may occur, and further improvement in workability is desired.

As described above, it is desired to develop a polymer material having excellent processability and excellent antibacterial or bactericidal action.

JP-A-61-246205 JP 2003-55108 A JP-A-6-9725

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a polymer material having excellent processability and excellent antibacterial or bactericidal action.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have incorporated a cationic functional group into a hyperbranched polymer that is a fine particle polymer that is excellent in solubility in a solvent or the like. The present invention has been completed by finding that it can be an antibacterial or bactericidal polymer material (ie, an antibacterial or bactericidal agent).

That is, the present invention
1. An antibacterial or bactericidal agent comprising a hyperbranched polymer containing a cationic functional group,
2. The antibacterial or bactericidal agent according to 1 above, wherein the hyperbranched polymer is a quaternary ammonium salt,
3. 2. The antibacterial or bactericidal agent according to 1 above, wherein the hyperbranched polymer is represented by the following formula (1):

[Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, carbon Represents an arylalkyl group having 6 to 20 atoms, or two or three substituents of R ₂ , R ₃ and R ₄ are bonded to each other by a linear, branched or cyclic alkylene group, and It may form a ring together with the nitrogen atom to be bonded, X ⁻ represents an anion, and A ₁ represents the formula (2)

(In the formula, A ₂ represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ₁ , Y ₂ , Y ₃ or Y _4. Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amino group, a carboxyl group, or a cyano group. Where n is the number of repeating unit structures and represents an integer of 2 to 100,000. ],
4). Wherein A ₁ is an antibacterial or disinfectant according to the 3, which is a structure represented by the following formula (3),

5). 6. The antibacterial or bactericidal agent according to 5 above, wherein in the formula (1), R ₂ , R ₃ and R ₄ are methyl groups,
6). In the formula (1), R ₁ is a hydrogen atom, R ₂ , R ₃ and R ₄ are methyl groups, Y is a bromine atom, and A ₁ is a structure represented by the formula (3). 6. The antibacterial or bactericidal agent according to 5 above,
7). The antibacterial or bactericidal agent according to 1 above, wherein the weight average molecular weight of the hyperbranched polymer measured in terms of polystyrene by gel permeation chromatography is 500 to 5,000,000,
8). The antibacterial or bactericidal agent according to 1, wherein the hyperbranched polymer has an average particle size of 1 nm to 100 nm,
9. A substrate formed by coating or kneading the antibacterial or bactericidal agent according to any one of 1 to 8 on the surface thereof;
10. The base material according to 9, wherein the base material is wood, paper, metal, fiber material, synthetic resin, or ceramics,
11. The antibacterial or bactericidal agent according to any one of 1 to 8 above is in the form of a solution, a viscous liquid, a gel, a spray, or a capsule in combination with or in combination with other components or materials. Antibacterial or disinfectant products,
12 A thin film containing the antibacterial or bactericidal agent according to any one of 1 to 8,
13. A substrate or support having at least one layer of the thin film as described in 11 above is provided.

The present invention provides a novel antibacterial or bactericidal polymer material (ie, an antibacterial or bactericidal agent) by binding a cationic functional group having an antibacterial or bactericidal function to a fine-grained hyperbranched polymer having a three-dimensional structure. Is.
In particular, a hyperbranched polymer having a quaternary ammonium salt structure has an excellent antibacterial or bactericidal action.
The antibacterial or bactericidal agent of the present invention has a fine particle structure in which a large number of quaternary ammonium salts are coordinated three-dimensionally to one molecule of the hyperbranched polymer because the terminal of the hyperbranched polymer has a quaternary ammonium salt structure. Thus, it exhibits excellent antibacterial or bactericidal action.

In addition, the antibacterial or bactericidal agent of the present invention can be immobilized on fiber materials, building materials, daily necessities, etc., and has characteristics such as being able to form a film by mixing with an aqueous solution, organic solvent, gel, etc. It can be applied to applications in the direction.
Thus, since it can be fixed to a base material or thinned, the antibacterial or bactericidal agent of the present invention is excellent in processability and can be applied to a wide range of antibacterial products.
For example, diapers, sanitary products, blood absorbents, wound dressings, other sanitary or medical products applied to the human body and animals such as external substrates, treatment of textiles such as clothing, bedding, duvets, curtains, kitchens Surface treatment of tools and equipment for processing and storage of foods and foods, gardening products such as civil engineering sealants, processing of agricultural products and building materials, processing, ships, airplanes, space materials and other items that require antibacterial action Can be applied anywhere.

The antibacterial or bactericidal agent of the present invention uses a hyperbranched polymer, and the hyperbranched polymer is known as a flexible particulate polymer. Therefore, when a thin film is formed on a substrate using a hyperbranched polymer, the surface area is larger than that of a thin film formed using a linear polymer. As a result, the immobilization using the hyperbranched polymer can be more precisely immobilized on the substrate surface than the linear polymer is immobilized on the surface. Due to this effect, an antibacterial material having a high effect can be produced by using a hyperbranched polymer.
In addition, since such antibacterial hyperbranched polymer has a hydrophobic part and a hydrophilic part, and is a flexible particle, it can suppress the growth of bacteria by freely changing its form so as to bring bacteria closer be able to.
It is well known that the antifouling effect and antibacterial effect of a photocatalyst are exhibited by the hydrophilic action of titanium oxide. On the other hand, it is also known that fluorine has a hydrophobic surface modification and exhibits an antibacterial action. Hyperbranched polymer can modify the surface by its thin film forming action, and can control the balance between hydrophilicity and hydrophobicity by the type and combination of terminal functional groups, so it can be an antibacterial material with various characteristics. it can.

Hereinafter, the present invention will be described in more detail.
The antibacterial or bactericidal agent according to the present invention is a hyperbranched polymer containing a functional group exhibiting antibacterial or bactericidal properties.
Examples of antibacterial or bactericidal functional groups include quaternary ammonium salts, pyridinium salts, phosphonium salts, pyridine compounds, organic halogen compounds, thiazoline compounds, phenols, imidazolium salts, chlorophenol compounds, pyridine thiol oxide salts. , A functional group containing a nitro group-containing morpholine compound, a triazine chloride compound and the like.
Among these, a functional group having a cationic property is preferably used.
For example, the hyperbranched polymer used in the present invention is a compound having a quaternary ammonium salt, pyridinium salt, imidazolium salt, piperazinium salt, morpholinium salt, or phosphonium salt structure.

The antibacterial or bactericidal agent according to the present invention is characterized in that a hyperbranched polymer is used.
Similar to the hyperbranched polymer, the advantage of the hyperbranched polymer over the dendrimer, which is a polymer having a dendritic (dendritic) structure, is its ease of synthesis. This is particularly advantageous in industrial production. In general, dendrimers are synthesized by repeated protection and deprotection, whereas hyperbranched polymers are synthesized by one-step polymerization of so-called AB _X type monomers having a total of 3 or more of two kinds of substituents in one molecule.
Differences in the properties of hyperbranched polymers relative to dendrimers include irregular branching and molecular weight distribution. Hyperbranched polymers have a mixture of linear and fully branched repeat units, whereas dendrimers have regularly branched repeat units without linear repeat units. Hyperbranched polymers also have a molecular weight distribution, whereas dendrimers have a single molecular weight.
These differences between hyperbranched polymers and dendrimers are that the structure of the hyperbranched polymer is random and irregular compared to spherical dendrimers.
If the dendrimer is a hard polymer, the hyperbranched polymer can be expressed as a soft polymer.

The hyperbranched polymer used in the present invention is not particularly limited, but a hyperbranched polymer containing a quaternary ammonium salt is preferable.

Further, the structure of the hyperbranched polymer is not particularly limited, but in the present invention, the structure represented by the formula (1) is preferably used.

A ₁ in the formula (1) represents the structure represented by the formula (2), and specific examples of the alkylene group of A ₂ in the formula (2) include a methylene group, an ethylene group, and a normal propylene group. And linear alkylene groups such as normal butylene group and normal hexylene group, and branched alkylene groups such as isopropylene group, isobutylene group and 2-methylpropylene group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic and bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms. For example, structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.

Examples of the alkyl group having 1 to 20 carbon atoms of Y ₁ , Y ₂ , Y ₃ or Y _{4 in} the formula (2) include a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, and a normal pentyl group. . Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, and normal pentyloxy group. Y ₁ , Y ₂ , Y ₃ or Y ₄ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
Further, A ₁ in the formula (1) preferably has a structure represented by the formula (3).

Examples of the straight, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ₂ , R ₃ and R _{4 in} the formula (1) include a methyl group, an ethyl group, an n-propyl group, i- Examples include propyl group, n-butyl group, sec-butyl group, n-octyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, cyclohexyl group, methylcyclohexyl group and the like.
As a combination of R ₂ , R ₃ and R ₄ , for example, when all are short carbon chains such as a methyl group or an ethyl group, R ₂ and R ₃ are short carbon chains such as a methyl group or an ethyl group. And R ₄ may be a long carbon chain such as an n-octyl group, an n-decyl group or an n-dodecyl group.

Examples of the arylalkyl group having 6 to 20 carbon atoms of R ₂ , R ₃ and R ₄ include a benzyl group, a phenethyl group and a 4-methylbenzyl group.

Two or three substituents of R ₂ , R ₃ and R ₄ are bonded to each other by a linear, branched or cyclic alkylene group, and together with the nitrogen atom bonded thereto, form a ring. For example, any two of R ₂ , R ₃ and R ₄ may be bonded together with an alkylene group to form a ring together with the nitrogen atom bonded thereto, and the other one may be Examples thereof include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 6 to 20 carbon atoms.
Examples of a ring formed by combining any _{two of} R ₂ , R ₃ and R _{4 with} an alkylene group and a nitrogen atom bonded to them include a piperazine ring and a piperazine ring.

Further, as an anion of X ⁻ , halogen ion, halite ion, hypohalite ion, nitrate ion, hyponitrite ion, sulfate ion, sulfite ion, thiosulfate ion, dithionite ion, phosphoric acid And ions, alkyl sulfonate ions having 1 to 5 carbon atoms, benzene sulfonate ions, alkyl sulfate ions having 1 to 5 carbon atoms, and the like.
Among these anions, halogen ions, phosphate ions, alkyl sulfonate ions having 1 to 5 carbon atoms, benzene sulfonate ions, alkyl sulfate ions having 1 to 5 carbon atoms, and the like are preferably used.

The hyperbranched polymer used in the present invention may be a single repeating unit structure or two or more repeating unit structures, and any of them may be used. For example, when the repeating unit structure is of two types, that is, a copolymer, the arrangement pattern of the copolymer may be a random copolymer, an alternating copolymer, or a block copolymer.

The hyperbranched polymer used in the present invention has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 500 to 5,000,000, preferably 1,000 to 1,000,000. More preferably, it is 2,000 to 500,000, and most preferably 3,000 to 100,000. Further, the dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, more preferably 1.2 to 5. 0.

The average particle size of the hyperbranched polymer used in the present invention is not particularly limited, but is preferably 1 nm to 100 nm.

The present invention also provides a substrate in which the antibacterial or bactericidal agent is coated on the surface or kneaded therein.
Examples of the base material include wood, paper, metal, fiber material, synthetic resin, and ceramics.
The base material formed by coating the antibacterial or bactericidal agent on the surface thereof or kneading the inside thereof is a solution in which the antibacterial or bactericidal agent of the present invention is dissolved to a concentration of 0.01 to 100% by mass, The solution is applied to the surface of the substrate by spraying, coating, or vapor-depositing on the surface of the substrate, or by immersing the substrate in the solution, and then dried at room temperature or under heating. Can be produced. It can also be produced by kneading the antibacterial or bactericidal agent of the present invention inside the substrate.

Further, the present invention provides the antibacterial or bactericidal agent in a form in which the antibacterial or bactericidal agent is added to or mixed with a solution, a viscous liquid, a gel, a spray, a capsule or the like in combination with or in combination with other components or materials. Products are also provided.
As the solution, a single solvent such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, ethanol, methanol or a mixed solvent thereof is used, and ethanol and methanol are particularly preferable.
Gels and viscous liquids include various synthetic polymers such as polyvinyl alcohol (PVA), carboxyvinyl polymer, sodium polyacrylate, polypropylene glycol, cellulose, alginic acid, xanthan gum, carrageenan, guar gum, pectin, chitosan, guard run, collagen, Examples include various natural polymers such as gelatin, and other supramolecules.

The present invention also provides a thin film containing the antibacterial or bactericidal agent.
The thin film is prepared by applying a solution prepared by dissolving the antibacterial or bactericidal agent of the present invention so as to have a concentration of 0.01 to 100% by mass on a base material, and evaporating the solvent to provide the antibacterial or bactericidal property on the base material. A thin film can be formed.
The application method is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, and a spray method. The method for evaporating the solvent is not particularly limited, and it may be dried at room temperature or under heating.

Examples of the substrate on which the thin film is formed include a substrate and a support.
Glass or plastic is used as the substrate and the support. A plastic film may be used. Examples of the plastic used include polystyrene, polyethylene, polypropylene, polymethyl methacrylate, polynorbornene, polycarbonate, polyamide, polyester, phenol resin, and epoxy resin.

The manufacturing method of the hyperbranched polymer used for this invention is demonstrated.
For example, the hyperbranched polymer represented by the above formula (1) is reacted with a tertiary amine compound after halogenating a hyperbranched polymer having a dithiocarbamate group represented by the following formula (4) at the molecular end. Can be manufactured.
The hyperbranched polymer having a dithiocarbamate group represented by the following formula (4) at the molecular end can be produced by the method described in International Publication No. 2006/093050.

(In the formula, R ₁ and A ₁ have the same meanings as defined in the formula (1), and R ₅ and R ₆ are each independently an alkyl group having 1 to 5 carbon atoms, 1 carbon atom. Or a hydroxylalkyl group having 5 to 5 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms, or R ₂ and R ₃ may be bonded to each other to form a ring together with the nitrogen atom bonded thereto.

The halogenation method is not particularly limited as long as it can convert a dithiocarbamate group to a halogen atom. Examples of halogenating agents that can be used in this reaction include chlorine, N-chlorosuccinimide, chlorinated isocyanuric acid, sulfuryl chloride, tertiary butyl hypochloride, phosphorus trichloride, phosphorus pentachloride, triphenylphosphine dichloride, and secondary chloride. Chlorinating agents such as copper and antimony pentachloride, bromine, N-bromosuccinimide, N-bromoglutarimide, N, N ′, N ″ -tribromoisocyanuric acid, sodium N, N′-dibromoisocyanurate, N, N'-bromoisocyanuric acid potassium, N, N'-dibromoisocyanuric acid, sodium N-bromoisocyanurate, N, N'-dibromohydantoin, N-bromohydantoin potassium, N, N'-bromohydantoin sodium, N- Brom-N'-methylhydantoin, 1,3-dibromo-5,5 -Dimethylhydantoin, 3-bromo-5,5'-dimethylhydantoin, 3-bromo-5,5'-dimethylhydantoin, 1-bromo-5,5'-dimethylhydantoin sodium, 1-bromo-5,5'- Brominating agents such as potassium dimethylhydantoin, sodium 3-bromo-5,5′-dimethylhydantoin, potassium 3-bromo-5,5′-dimethylhydantoin, iodine, N-iodosuccinimide, potassium iodate, periodate An iodinating agent such as potassium, periodic acid, iodic acid, etc. can be used, and the amount of the halogenating agent used is 1 to 20 times molar equivalent to the number of dithiocarbamate groups in the hyperbranched polymer, preferably It may be 1.5 to 15 times molar equivalent, more preferably 2 to 10 times molar equivalent. The conditions of the reaction, the reaction time of 0.01 to 100 hours, from 300 ° C. to not a reaction temperature of 0, is properly selected. Preferably from 0.1 reaction time 10 hours, 0.99 ° C. to not reaction temperature 20.

The reaction for substituting the dithiocarbamate group at the molecular end with a halogen atom is preferably carried out in water or an organic solvent. The solvent to be used is preferably a solvent capable of dissolving the hyperbranched polymer having a dithiocarbamate group and the halogenating agent. In addition, it is preferable that the solvent is the same as the solvent used when producing the hyperbranched polymer having a dithiocarbamate group because the reaction operation is simplified.

As the halogenation method, a reaction performed by heating and refluxing using a halogenating agent such as bromine in an organic solvent solution is preferable. The organic solvent may be any organic solvent that does not significantly inhibit the progress of this reaction, such as acetic acid and other organic acid solvents, benzene, toluene, xylene, ethylbenzene, 1,2-dichlorobenzene, and other aromatic hydrocarbons, tetrahydrofuran. Ether compounds such as diethyl ether, ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane, normal heptane, normal hexane, cyclohexane, etc. Can be used. These solvents may be used alone or in combination of two or more. The mass of the hyperbranched polymer having a dithiocarbamate group at the molecular end is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably 10 to 10 times. It is preferable to use 50 times mass organic solvent. In this reaction, it is necessary to sufficiently remove oxygen in the reaction system before the start of the reaction, and the inside of the system may be replaced with an inert gas such as nitrogen or argon. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 200 ° C. The reaction time is preferably 0.1 to 5 hours, and the reaction temperature is 20 to 150 ° C.
After the reaction, it is desirable to decompose the halogenating agent remaining in the system. In this case, an aqueous solution of a reducing agent such as sodium thiosulfate and sodium sulfite, or sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. An alkaline aqueous solution can be used. Moreover, you may make it react with the compound containing unsaturated bonds, such as ethylene, propylene, butene, and cyclohexene. The amount used may be 0.1 to 50 equivalents, preferably 0.5 to 10 equivalents, more preferably 1 to 3 equivalents, relative to the halogenating agent used. The hyperbranched polymer having a halogen atom at the molecular end obtained by the reaction as described above can be separated from the solvent from the reaction solution by solvent distillation or solid-liquid separation. Moreover, the hyperbranched polymer which has a halogen atom in a molecular terminal can be precipitated by adding a reaction solution in a poor solvent, and it can also collect | recover as powder.
In the hyperbranched polymer containing a halogen atom at the molecular end, a part of the molecular end may remain as a dithiocarbamate group.

The hyperbranched polymer represented by the formula (1) can be obtained by reacting a tertiary amine compound with a hyperbranched polymer having a halogen atom at the molecular end.
The tertiary amine compounds that can be used in this reaction include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, N, N-dimethyl-N-octylamine, N, N-diethyl-Nn-decylamine. N, N-dimethyl-Nn-dodecylamine, N, N-dimethyl-Nn-tetradecylamine, N, N-dimethyl-Nn-hexadecylamine, N, N-dimethyl-N- aliphatic amines such as n-octadecylamine, N, N-dimethyl-Nn-eicosylamine, N, N-dimethyl-Nn-dodecylamine, N, N-dimethyl-N-benzylamine, N, And arylalkylamines such as N-dimethyl-N-phenethylamine and N, N-dimethyl-N- (4-methylbenzyl) amine.

The amount of the tertiary amine compound that can be used in these reactions is 0.1 to 20 times the molar equivalent of the halogen atom in the hyperbranched polymer having a halogen atom at the molecular end, preferably 0.8. It may be 5 to 10 times molar equivalent, more preferably 1 to 5 times molar equivalent. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C. The reaction time is preferably 0.1 to 10 hours and the reaction temperature is 20 to 150 ° C.

The reaction between the halogen atom at the molecular end and the tertiary amine compound can be performed in water or an organic solvent solution in the presence or absence of a base. The solvent used is preferably a solvent capable of dissolving the hyperbranched polymer having a halogen atom and a tertiary amine compound. Furthermore, a hyperbranched polymer having a halogen atom and a tertiary amine compound can be dissolved, but a solvent that does not dissolve a hyperbranched polymer having an ammonium group at the molecular end is easy to isolate and is more preferable. .

Any organic solvent may be used as long as it does not significantly inhibit the progress of this reaction. Water, organic acid solvents such as acetic acid, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, 1,2-dichlorobenzene, etc. Ether compounds such as tetrahydrofuran and diethyl ether, ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, chloroform, dichloromethane, 1,2-dichloroethane, normal heptane, normal hexane, cyclohexane, dimethylformamide, dimethylacetamide, Aliphatic hydrocarbons such as N-methylpyrrolidone can be used. These solvents may be used alone or in combination of two or more. The amount used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably the mass of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use an organic solvent having a mass of 10 to 50 times. In this reaction, it is necessary to sufficiently remove oxygen in the reaction system before the start of the reaction, and the inside of the system may be replaced with an inert gas such as nitrogen or argon. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 200 ° C. The reaction time is preferably 0.1 to 5 hours and the reaction temperature is 20 to 150 ° C.

The hyperbranched polymer having an ammonium group at the molecular end of the present invention obtained by the reaction method as described above can be separated from the solvent from the reaction solution by solvent distillation or solid-liquid separation. In addition, the hyperbranched polymer can be precipitated by adding the reaction solution into a poor solvent and recovered as a powder.
In the hyperbranched polymer having an ammonium group, a part of the molecular terminal may remain as a halogen atom.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by this.
In the following examples, the following apparatuses were used for measuring physical properties of samples.

(1) Liquid chromatography apparatus: Agilent 1100 Series
Column: Inertsil ODS-2
Column temperature: 40 ° C
Solvent: acetonitrile / water = 60/40 (volume ratio)
Detector: RI
(2) Gel permeation chromatography device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex KF-805L + KF-804L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
(3) FT-IR
Apparatus: NEXUS670 manufactured by Nicorey Japan
(4) Thermogravimetric analysis device: TG8120 manufactured by Rigaku Corporation
Temperature rising rate: 10 ° C./min Air volume: 60 ml / min (5) Melting point analyzer Device: DSC8230 manufactured by Rigaku Corporation
Temperature rising rate: 2 ° C./min Nitrogen amount: 60 ml / min (6) Elemental analysis (carbon, hydrogen, nitrogen)
Apparatus: Perkin Elmer PE2400II
Combustion tube temperature: 975 ° C
(7) Elemental analysis (sulfur)
Pretreatment equipment: Automatic sample combustion equipment manufactured by Diane Instruments Co., Ltd. AQF-100 type Combustion tube temperature: 1000 ° C
Analysis device: ICS-1500, manufactured by Nippon Dionex Co., Ltd.
Column: Dionex AS12A
Eluent: sodium carbonate 2.7 mM-sodium bicarbonate 0.3 mM
(8) Elemental analysis (sodium)
Equipment: Vista-Pro, manufactured by SII Nano Technology Co., Ltd.

Reference Example 1: Synthesis of a styrene-based hyperbranched polymer having a dithiocarbamate group at the molecular end In a 300 mL reaction flask, 108 g of N, N-diethyldithiocarbamylmethylstyrene and 72 g of toluene were charged and stirred to obtain a pale yellow transparent solution. After the preparation, the reaction system was purged with nitrogen. A 100 W high pressure mercury lamp (manufactured by Sen Special Light Source Co., Ltd., HL-100) was turned on from the middle of this solution, and a photopolymerization reaction by internal irradiation was carried out for 12 hours at a temperature of 30 ° C. with stirring. Next, this reaction solution was added to 3000 g of methanol to reprecipitate the polymer in a highly viscous lump state, and then the supernatant was removed by decantation. Furthermore, after this polymer was redissolved in 300 g of tetrahydrofuran, this solution was added to 3000 g of methanol to reprecipitate the polymer in a slurry state. This slurry was filtered and vacuum-dried to obtain 48 g of a hyperbranched polymer represented by the following formula (5) as a white powder. The weight average molecular weight Mw measured by gel permeation chromatography in terms of polystyrene was 20,900, and the degree of dispersion Mw / Mn was 4.9. The elemental analysis was 64.6% by mass of carbon, 7.4% by mass of hydrogen, 5.0% by mass of nitrogen and 25.3% by mass of sulfur.

Reference Example 2: Synthesis of a styrene-based hyperbranched polymer having a halogen atom at the molecular end 10 g of the hyperbranched polymer represented by the above formula (5) synthesized in Reference Example 1 and chloroform were added to a 300 mL reaction flask equipped with a reflux tower. 50 g was charged and the reaction system was purged with nitrogen. To this, 16.0 g of bromine [manufactured by Junsei Chemical Co., Ltd.] dissolved in 50 g of chloroform was added dropwise and refluxed for 3 hours. After cooling to a temperature of 30 ° C., the produced orange precipitate was filtered off.
Saturated brine and 20% by weight sodium thiosulfate were added to wash the organic phase. This solution was dropped into 500 g of methanol to perform reprecipitation. The obtained yellow powder was again dissolved in 40 g of chloroform, dropped into 500 g of methanol, reprecipitated, and the obtained colorless powder was dried to obtain 4.6 g of a hyperbranched polymer represented by the following formula (6). Got. The weight average molecular weight Mw measured by gel permeation chromatography in terms of polystyrene was 6,600, and the degree of dispersion Mw / Mn was 2.2. Elemental analysis was 50.2 mass% carbon, 3.8 mass% hydrogen, less than 1.0 mass% nitrogen, and 33.2 mass% bromine.

Reference Example 3: Synthesis of a styrene-based hyperbranched polymer having a trimethylammonium group at the molecular terminal A hyperbranched polymer represented by the above formula (6) synthesized in Reference Example 2 was added to a 300 mL reaction flask equipped with a reflux tower. 50 g and 3.0 g of N, N′-dimethylformamide were charged, and 0.59 g of a 30 mass% trimethylamine aqueous solution [manufactured by Tokyo Chemical Industry Co., Ltd.] was added. At this time, the system was suspended. The system was purged with nitrogen and heated at 80 ° C. for 6 hours. After cooling to a temperature of 30 ° C., the resulting precipitate was washed with acetone. This solid was dissolved in 3.0 g of water, reprecipitated with 20 g of acetone, and dried to obtain 0.33 g of a hyperbranched polymer represented by the following formula (7) (light brown powder).

Example 1: Antibacterial activity of a styrene-based hyperbranched polymer having a trimethylammonium group at the molecular end 2% glucose [0.1 M phosphate buffer (dipotassium hydrogen phosphate, potassium dihydrogen phosphate, PH = 5) in 100 mL D (+)-glucose 2 g] and 4% acetate (0.1 M phosphate buffer (dipotassium hydrogen phosphate, potassium dihydrogen phosphate, PH = 5) in 100 mL 4 g of sodium acetate trihydrate Complete Supplement Mixture (CSM) medium containing 0.85 g yeast nitrogen base, W / O amino acid-ammonium sulfate [manufactured by DIFCO], 0.31 g CSM [manufactured by BIO 101], 0.1M phosphoric acid Buffer (dipotassium hydrogen phosphate, potassium dihydrogen phosphate, PH = 5) 1L The bacterial solution pre-cultured for 3 days with 10 mL of PH = 7] was diluted with CSM medium to prepare a bacterial solution (10 ⁴ -10 ⁶ cells / mL). The number of germs was measured under an inverted microscope LH50A (Olympus, x100-400).
Next, a hyperbranched polymer having a trimethylammonium group represented by the above formula (7) on a 96-well microplate [manufactured by Corning, polystyrene], a hyperbranched polymer having a halogen atom represented by the above formula (6), After adding 20 μL (final concentration 10 μg / mL) of the hyperbranched polymer having a dithiocarbamate group represented by the formula (5) and chloramphenicol, 180 μL of the diluted bacterial solution is added to the same plate at 25 ° C. The stationary culture was performed for 4 days. The degree of growth (antibacterial activity) of each bacterium was objectively judged (effective at 90% inhibition or more).
The test bacteria were Gram-positive bacteria Bacillus subtilis (BS) (PCI-219), Staphylococcus aureus (Sa) (IFO-12732), tomato ulcer fungus Clavibacter michiganensis subsp. Michiganensis (Cm) (MAFF301037), Gram-negative bacteria of sugar beet soft rot, Erwinia carotovora subsp. Carotovora (EC) (MAFF301052), Solanaceae plant blight fungus Ralstonia solanacearum (Rs) (MAFF301037), rice blight bacterial fungus Burkholderia glumae (Bg) (MAFF301169), Citrus ulcer fungus Xantampon rump. citri (Xc) (MAFF301078) and Escherichia coli Escherichia coli (IFO-3972) were used.
The test sample solution was prepared by adding 1 mg of a hyperbranched polymer having a trimethylammonium group represented by the above formula (7) to 2.5 μL of emulsifier (Solpol [3005XL, manufactured by Toho Chemical Industry Co., Ltd.]: acetone: DMSO: xylene = 1: 3: It was dissolved in 100 μL of acetone containing 3: 3). This was mixed and diluted with 900 μL of water to obtain a test solution (1000 ppm 1 mL).
The hyperbranched polymer having a trimethylammonium group represented by the formula (7) synthesized in Reference Example 3 (final concentration: 10 μg / mL) is a tomato ulcer, Staphylococcus aureus, Bacillus subtilis, citrus ulcer, It showed antibacterial action against pathogenic bacteria and Escherichia coli (Table 1). The subject chloramphenicol (final concentration 10 μg / mL) exhibited antibacterial activity against tomato ulcer disease bacteria, Staphylococcus aureus, Bacillus subtilis, rice wilt bacteria disease, citrus ulcer disease bacteria, and Escherichia coli (Table 1). The hyperbranched polymer having a trimethylammonium group represented by the formula (7) showed an antibacterial profile different from that of chloramphenicol.
No antibacterial activity was observed in the hyperbranched polymer having a dithiocarbamate group represented by the formula (5) synthesized in Reference Example 1 and the hyperbranched polymer having a halogen atom represented by the formula (6).

Example 2: Cross-linking action of styrene-based hyperbranched polymer having trimethylammonium group at the molecular end to E. coli The cross-linking action of Eperbranch polymer having trimethylammonium group represented by the above formula (7) to E. coli was determined by the following test method. investigated. E. coli Escherichia coli (IFO 3972) was precultured in LB medium (yeast extract 5 g / L, tryptone 10 g / L, sodium chloride 5 g / L, PH = 7) at 30 ° C. for 1 day, diluted with LB medium to obtain a bacterial solution ( 10 ⁴ pieces / ml). The number of germs was measured under an inverted microscope LH50A (Olympus, x100-400). After adding a hyperbranched polymer having a trimethylammonium group represented by the above formula (7) to a 96-well microplate [Corning Inc., polystyrene] 10 μL at a final concentration of 10 μg / mL, 90 μL of a bacterial solution is added, After standing at room temperature (23-25 ° C.) for 2 hours, the absorbance at 650 nm was precisely measured using a 96-well microplate reader [Spectramax 190, manufactured by Nihon Molecular Devices Co., Ltd.]. Further, the toxicity to Escherichia coli at that time was measured using WST-8 (manufactured by Kishida Chemical Co., Ltd.) according to the attached instructions. That is, 10 μL of 5 mM WST-8 reagent was added to each well and heated at 37 ° C. for 3 hours. The formazan dye produced was precisely measured for absorbance at 450 nm using a 96-well microplate reader. The degree of crosslinking and cytotoxicity was determined by the rate of decrease of each absorbance calculated using the calculation formula (1).
Formula (1)
Decrease rate (%) = [[absorbance of control] − [absorbance of hyperbranched polymer having trimethylammonium group represented by the formula (7)] / [absorbance of control]] × 100
The hyperbranched polymer having a trimethylammonium group represented by the formula (7) reduced the absorbance at 650 nm by 47.7% at a final concentration of 10 μg / mL, that is, exhibited a crosslinking action (Table 2). At this time, the hyperbranched polymer having a trimethylammonium group represented by the formula (7) did not change the absorbance with respect to Escherichia coli, and thus did not show toxicity against Escherichia coli (Table 2).
In this example, the hyperbranched polymer having a trimethylammonium group represented by the above formula (7) is first adsorbed to the fungus, and at the same time, the fungus and the fungus are crosslinked to collect the fungus around the hyperbranched polymer. This shows that a number of cationic functional groups at the ends of the hyperbranched polymer act on the cell membrane to exert an antibacterial effect. That is, this example shows that a hyperbranched polymer having a trimethylammonium group is a new type of antibacterial or bactericidal agent having antibacterial properties triggered by a fungus crosslinking action.

Example 3: Immobilization of a styrene-based hyperbranched polymer having a trimethylammonium group at a molecular end on a glass substrate 100 μL of a methanol solution containing 10% by mass of a hyperbranched polymer having a trimethylammonium group represented by the formula (7) Was added dropwise to a glass white edge polish No. 276 × 26 mm thickness 1.0-1.2 mm (Matsunami Glass Industry Co., Ltd.) mounted on a spin coater 1H-D7 (Mikasa Co., Ltd.) and spin coated (300 rpm at 5 rpm). Second, 2500 rpm was applied for 25 seconds). Determination of immobilization is performed when 3 μL of pure water is dropped by the water contact angle measurement method using the automatic contact angle meter CA-Z type (manufactured by Kyowa Interface Science Co., Ltd.) for the wettability of the glass substrate surface-treated with the hyperbranched polymer trimethylamine. Was measured at 23 ° C. after 1, 3 and 5 minutes of dropping.
As shown in FIG. 1, the contact angle (indicated by ● in FIG. 1) of the glass substrate surface-treated with the hyperbranched polymer having a trimethylammonium group represented by the formula (7) is lowered, and the glass is made hydrophilic. Since the surface was modified, it was confirmed that the hyperbranched polymer having a trimethylammonium group represented by the formula (7) was immobilized on the glass substrate.

Example 4 Addition of a styrene-based hyperbranched polymer having a trimethylammonium group at a molecular end to a gel 1% polyvinyl alcohol containing 0.5% by mass of a hyperbranched polymer having a trimethylammonium group represented by the formula (7) [Kuraray Poval PVA117 Completely Saponified] 3 mL of a transparent aqueous solution was placed in a polystyrene container [ASONE ABS non-charged square case 1 type 3.6 cm × 3.6 cm × 1.4 cm] and frozen at −20 ° C. overnight. Thawing. This freezing / thawing operation was repeated 5 times.
Since a white gel was formed by this operation, a hyperbranched polymer having a trimethylammonium group could be added to the gel.

It is the figure which showed fixation on the glass substrate of the hyperbranched polymer which has a trimethylammonium group represented by said Formula (7).

Claims

An antibacterial or bactericidal agent comprising a hyperbranched polymer containing a cationic functional group.
The antibacterial or bactericidal agent according to claim 1, wherein the hyperbranched polymer is a quaternary ammonium salt.
The antibacterial or bactericidal agent according to claim 1, wherein the hyperbranched polymer is represented by the following formula (1).

[Wherein R 1 represents a hydrogen atom or a methyl group, and R 2 , R 3 and R 4 each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, carbon Represents an arylalkyl group having 6 to 20 atoms, or two or three substituents of R 2 , R 3 and R 4 are bonded to each other by a linear, branched or cyclic alkylene group, and It may form a ring together with the nitrogen atom to be bonded, X − represents an anion, and A 1 represents the formula (2)

(In the formula, A 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y 1 , Y 2 , Y 3 or Y 4. Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amino group, a carboxyl group, or a cyano group. Where n is the number of repeating unit structures and represents an integer of 2 to 100,000. ].
The antibacterial or bactericidal agent according to claim 3, wherein the A 1 has a structure represented by the following formula (3).
In the formula (1), R 2, R 3 and R 4 are, antibacterial or disinfectant according to claim 3, characterized in that a methyl group.
In the formula (1), R 1 is a hydrogen atom, R 2 , R 3 and R 4 are methyl groups, X is a bromine atom, and A 1 is a structure represented by the formula (3). The antibacterial or bactericidal agent according to claim 5, wherein
The antibacterial or bactericidal agent according to claim 1, wherein the hyperbranched polymer has a weight average molecular weight of 500 to 5,000,000 measured by gel permeation chromatography.
The antibacterial or bactericidal agent according to claim 1, wherein the hyperbranched polymer has an average particle size of 1 nm to 100 nm.
A base material obtained by coating the surface of the antibacterial or bactericidal agent according to any one of claims 1 to 8 or kneading the antibacterial or bactericidal agent therein.
The base material according to claim 9, wherein the base material is wood, paper, metal, fiber material, synthetic resin, or ceramics.
The antibacterial or bactericidal agent according to any one of claims 1 to 8 is in the form of a solution, a viscous liquid, a gel, a spray or a capsule in combination with or in combination with other components or materials. Features antibacterial or disinfectant products.
A thin film comprising the antibacterial or bactericidal agent according to any one of claims 1 to 8.
The board | substrate or support body which has at least 1 layer of the thin film of Claim 11.