JP3171691B2 - Copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymer and a method for producing the same. ADVANTAGE OF THE INVENTION According to this invention, the antimicrobial copolymer which is excellent in bactericidal power, has high safety and stability, and can maintain the effect over a long period of time is provided.

[0002] The antibacterial polymer of the present invention is, for example,
Sterilization of cooling water, pool water, etc., antifouling compositions such as slime control, fishing nets, ship bottoms, underwater structures, food packaging materials, building materials, agricultural materials, medical supplies, oral materials (toothbrushes, toothpastes, etc.) , Eyeglass frames, cosmetics, clothing,
It can be used for a wide range of applications such as household goods.

[0003]

2. Description of the Related Art Among conventional antimicrobial compounds, those having a low molecular weight are simply used as a mixture with materials (for example, resins) constituting various products. Elution and the accompanying decrease in antibacterial activity are inevitable, and furthermore, there is a problem of toxicity to a living body coming into contact with the product.

[0004] In order to solve these problems, development of polymers having antibacterial properties has been promoted. Known antibacterial polymers include, for example, those composed of a repeating unit represented by the general formula (3) (Japanese Patent Laid-Open No. 61-100254) and those composed of a repeating unit represented by the general formula (4) ( JP 61
-246205).

[0005]

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[In the formula, R ¹⁰ represents a methyl group or an ethyl group, and R ¹¹ represents an alkyl group having 3 to 30 carbon atoms. ]

[0007]

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Wherein R ¹² is the same or different and has 1 to 1 carbon atoms
4 represents an alkyl group, R ¹³ represents an alkyl group having 14 to 20 carbon atoms, and X ⁻ represents an anion. ]

However, these known antibacterial polymers are not satisfactory in their antibacterial activity.

The production of the above antibacterial polymer is carried out by reacting a polymer having a reactive chloro group on the side chain with a tertiary amine and replacing the reactive chloro group with a tertiary amine. It is difficult to completely perform the substitution, and therefore, many active functional groups containing a chlorine atom remain in the molecule, so that the stability of the antibacterial polymer itself and the safety to the human body are reduced. There's a problem.

In order to solve such problems, an antibacterial polymerizable monomer is synthesized, and an antibacterial polymer is produced by copolymerizing the polymerizable monomer with another monomer. For example, an antifouling paint containing a copolymer containing a monomer represented by the general formula (5) as an active ingredient is also known (JP-A-2-64167).

[0012]

Embedded image

Wherein R ¹⁴ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and R ¹⁵ and R ¹⁶
Represents an alkyl group having 1 to 3 carbon atoms, R ¹⁷ represents a hydrogen atom or a methyl group, B represents O—CO or O—CH ₂ , and X represents a monovalent anion. ]

According to the report of Senuma et al., Chloromethylstyrene and cetyldimethylamine [C ₁₆ H ₃₃ N (C
H ₃ ) ₂ ] and the fourth compound represented by the general formula (6)
A quaternary ammonium salt monomer is obtained, and this is copolymerized with acrylonitrile to obtain a polymer [(Research Report No. 159 (1988), pp. 17-2)
2]. However, these polymers also do not have sufficiently satisfactory antimicrobial activity.

[0015]

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Further, in US Pat. No. 4,092,201, for example, a cationic monomer represented by the formula (7) is obtained and polymerized to produce a polymer. The polymer may be used as an adsorbent or It only describes that it is effective in improving antistatic properties, dye acceptance, etc., but does not disclose any use of it for antibacterial use. In addition, the above-mentioned monomer is easily hydrolyzed because the functional group containing a polymerizable vinyl group and a cationic group is bonded via an ester group. Therefore, in a polymer derived from the cationic monomer, a cationic group ( There is a problem that the side chain containing a diammonium group) is desorbed and eluted from the polymer main chain, and the function is reduced.

[0017]

Embedded image

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antibacterial copolymer having excellent bactericidal activity, high safety and stability, and which can maintain its efficacy over a long period of time. It is in.

[0019]

The present invention provides a process for producing a copolymer having a structural unit derived from a non-crosslinkable or crosslinkable vinyl monomer or a mixture thereof and a structural unit represented by the general formula (1). According to.

[0020]

Embedded image [Wherein, R ¹ represents a hydrogen atom, a methyl group, a chloro group or a cyano group, R ² represents an alkylene group having 1 to 4 carbon atoms, R ³ represents an alkylene group having 3 to 10 carbon atoms, and R ⁴ represents a carbon atom. R ^{5 to} R ⁸ are the same or different and have 1 to 3 carbon atoms.
And the alkyl group may contain a substituent. A is a methylene group, which may have a substituent phenylene _{group, -CH 2 O -, - CH} 2 CH 2 O -, - CO-,
—CO—N (R ⁹ ) —, (R ⁹ represents a hydrogen atom or a methyl group) or a vinylene group. m represents 0 or 1.
X and Y are the same or different and represent a monovalent anion, or both represent a divalent anion. ]

In the compound of the above general formula (1), R ³
Of the alkylene groups represented by, those having 4 and 6 carbon atoms are particularly preferred from the viewpoint of antibacterial properties. Among the alkyl groups represented by R ⁴ , those having 10, 12 and 14 carbon atoms are particularly preferred from the viewpoint of antibacterial properties.

In the above general formula (1), examples of the substituent of the phenylene group which may have a substituent represented by A include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Group, ethyl group, propyl group, lower alkyl group such as butyl group, methoxy group, ethoxy group,
Examples thereof include lower alkoxy groups such as a propoxy group and a butoxy group. The anion represented by X and Y is not particularly limited as long as it can neutralize a positive charge. Examples thereof include chloride ion, bromine ion, iodine ion, nitrate ion, perchlorate ion, acetate ion, and methyl ion. Monovalent anions such as sulfate ion, benzenesulfonate ion, chlorobenzenesulfonate ion and toluenesulfonate ion, and divalent anions such as sulfate ion and methylphosphate ion can be exemplified.

In the general formula (2), the group represented by A is a methylene group, a phenylene group which may have a substituent, -CO-, -CO-N (R ⁹ )-, (R ⁹ is Same as above) or the compound (2a) which is a vinylene group can be produced, for example, by reacting a compound represented by the general formula (8) with a compound represented by the general formula (9).

[0024]

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Wherein R ^{3 to} R ⁸ and X are as defined above. ]

[0026]

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Wherein R ¹ , R ² , m and Y are as defined above. A ¹ is a methylene group, —CO—, —CO—N (R ⁹ )
-, (R ⁹ is as defined above) or a vinylene group. ]

The above reaction is usually carried out in a solvent, if necessary, with heating. The solvent is not particularly limited as long as it does not affect the reaction, and examples thereof include alcohols such as methanol, ethanol and propanol, ethers such as dimethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, and dichloromethane. And halogenated hydrocarbons such as carbon tetrachloride, acetone, ethyl acetate, dimethyl sulfoxide, dimethylformamide and the like. At the time of the reaction, since both the target compound (2a) and the compound (9) are polymerizable, ordinary polymerization inhibitors such as hydroquinone and catechol may be added to the reaction system as needed. The compounding ratio of the compound (8) and the compound (9) is not particularly limited and can be appropriately selected from a wide range. The compound (9) is usually used in a molar amount of about 0.7 to 1.2 times, preferably 0.9 to 1.0 times the compound (8).
What is necessary is just to use about twice mol.

The mono-quaternary ammonium salt derivative represented by the general formula (8) can be obtained, for example, by adding a compound represented by the general formula (11) to a lower alkyl-substituted alkanediamine derivative represented by the general formula (10) without using a solvent. Alternatively, it is produced by reacting with heating in a solvent, if necessary.

[0030]

Embedded image

Wherein R ³ and R ^{5 to} R ⁸ are the same as above. ]

[0032]

R ⁴ X [R ⁴ is the same as above] (11)

The solvent is not particularly limited as long as it does not affect the reaction, and examples thereof include lower alcohols such as methanol and ethanol, nitriles such as acetonitrile, and ethers such as tetrahydrofuran. The compounding ratio of the compound (10) and the compound (11) is not particularly limited, but is usually about 1.0 to 5 times, preferably 1.2 to 5 times, the molar amount of the compound (10) with respect to the compound (11).
It may be about 4 times the mole.

Specific examples of the compound (10) include, for example, N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,4 -Butanediamine, N, N, N ', N'-tetramethyl-1,5-pentanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N, N ' , N'-tetramethyloctanediamine, N, N, N ', N'-tetramethyldecanediamine, N,
N, N ', N'-tetraethylethylenediamine, N, N,
N ′, N′-tetraethyl-1,3-propanediamine, N,
N, N ', N'-tetraethyl-1,4-butanediamine, N,
N, N ', N'-tetraethyl-1,5-pentanediamine,
N, N, N ', N'-tetraethyl-1,6-hexanediamine and the like can be mentioned. Specific examples of the compound (11) include, for example, alkyl chlorides, alkyl bromides, alkyl iodides, alkyl benzenesulfonates, alkyl chlorobenzenesulfonates, alkyltoluenesulfonates having about 6 to 18 carbon atoms, and the like. Can be mentioned.

Specific examples of compound (9) include, for example, allyl halide or methallyl halide in which the halogen atom is chlorine, bromine or iodine, allyl benzenesulfonate, allyl chlorobenzenesulfonate, allyl toluenesulfonate, chloro Methyl styrene, chloromethyl vinyl ketone, bromomethyl vinyl ketone, methallyl benzenesulfonate, methallyl chlorobenzenesulfonate, methallyl toluenesulfonate, α-methyl (chloromethyl) styrene, α-chloro (chloromethyl) styrene,
α-cyano (chloromethyl) styrene, α-chloromethylacrylonitrile, N-2-chloroethylacrylamide, N-2-bromoethylacrylamide, N-methyl-N-2-bromoethylacrylamide, N-2-bromoethylmethacrylamide , N-methyl-N-2-bromoethyl methacrylamide, N-2-tosyloxyethyl acrylamide, N-methyl-N-2-tosyloxyethyl methacrylamide and the like.

Furthermore in the general formula (2), the group represented by A is _{-CH 2 O -, - CH 2} CH 2 O- , compound (2b) may include compounds represented by the general formula (12) And a compound represented by the general formula (13).

[0037]

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Wherein R ^{2 to} R ⁸ , X and Y are the same as above. ]

[0039]

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Wherein R ¹ is as defined above. A ² represents a methylene group or an ethylene group. Z is a halogen atom, carbon number 1
A lower alkoxy group, a lower acyloxy group having 2 to 5 carbon atoms, a benzenesulfonyloxy group, a chlorobenzenesulfonyloxy group, a tosyloxy group or a methanesulfonyloxy group. Examples of the lower acyloxy group include acetyloxy, propionyloxy, butyryloxy, and valeryloxy.

The above reaction is usually carried out in a solvent in the presence of a base, if necessary, with heating. The solvent is not particularly limited as long as it does not affect the reaction, for example,
Ether, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, dimethylsulfoxide and the like can be mentioned. At the time of the reaction, since both the target compound (2b) and the compound (13) are polymerizable, a usual polymerization inhibitor such as hydroquinone or catechol may be added to the reaction system as needed. The amount of the base used is not particularly limited, but may be generally about the stoichiometric amount.
The compounding ratio of the compound (12) to the compound (13) is not particularly limited, but the compound (12) is usually used in an amount of about 0.7 to 1.2 times, preferably about 0.9 to 1.0 times, the compound (13). .

As the base, any conventional one can be used without any particular limitation. Examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide and sodium carbonate, and organic bases such as pyridine, piperidine, diisopropylamine, triethylamine and diazabicyclooctane. Can be mentioned.

Specific examples of the compound (13) include, for example, allyl halide or methallyl halide in which the halogen atom is chlorine, bromine or iodine, 4-bromo-1-butene, 3-butenyl toluenesulfonic acid, benzenesulfonic acid. And esters of toluenesulfonic acid or chlorobenzenesulfonic acid with allyl alcohol or methallyl alcohol, and 2,3-dichloropropene.

The compound (12) is a known substance and can be produced, for example, by reacting the compound (8) with a compound represented by the general formula (14).

[0045]

Embedded image HO—R ² Y wherein R ² and Y are the same as above. ] (14)

This reaction is usually carried out in a solvent which does not affect the reaction, if necessary, with heating. The compounding ratio of the compound (8) to the compound (14) is not particularly limited.
It may be used in an amount of about 3 moles, preferably about 1.2 to 2 moles. Specific examples of compound (14) include, for example, 2-
Halogeno-1-ethanol, 3-halogeno-1-propanol, 4-halogeno-1-butanol, 3-halogeno-2-methyl-1-propanol (where halogen atoms are chlorine, bromine, iodine, etc.), benzenesulfonic acid -2-
Examples thereof include hydroxyethyl, 2-hydroxyethyl toluenesulfonic acid, 3-hydroxypropyl toluenesulfonic acid, and 4-hydroxybutyl toluenesulfonic acid.

Further, compound (12) can be produced, for example, as follows. That is, a compound represented by the general formula (14a) in which the hydroxyl group of the compound (14) is protected by a suitable functional group W is obtained, and the compound is reacted with the compound (8) to obtain a compound represented by the general formula (12)
Compound (12) can be produced by obtaining the compound represented by a) and further hydrolyzing the compound. W
Examples of the functional group represented by include an acetyl group, a tetrahydropyranyl group, a methoxymethyl group, a benzenesulfonyl group, and a toluenesulfonyl group.

[0048]

Embedded image WO-R ² Y (14a)

[Wherein R ² and Y are the same as above. W represents a functional group. ]

[0050]

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Wherein R ^{2 to} R ⁸ , X, Y and W are the same as above. ]

The reaction between compound (8) and compound (14a) is carried out in a suitable solvent, if necessary, with heating.
The solvent is not particularly limited as long as it does not affect the reaction. For example, the same solvent as used in the synthesis of compound (8) can be used. The amount of compound (14a) to be used is not particularly limited and can be appropriately selected from a wide range, but is usually about 1.0 to 3 moles, preferably 1.2 to 2 moles per mole of compound (8).
What is necessary is just to make it about 2 times mol. Specific examples of compound (14a) include, for example, 2-halogenoethyl acetate, 2-halogenoethyl tetrahydropyranyl ether, 4-halogenobutyl toluenesulfonate (here, halogen atoms are chlorine, bromine, iodine, etc.), ethylene glycol Bisbenzenesulfonic acid ester, ethylene glycol bistoluenesulfonic acid ester and the like can be mentioned.

The hydrolysis of the compound (12a) is carried out according to a usual method. For example, the compound (12a) can be easily converted to the compound (12) by heating it in diluted hydrochloric acid as needed.

The compound (2) and its intermediate obtained in each of the above reactions can be isolated and purified by usual means such as filtration, extraction, concentration and recrystallization.

The copolymer of the present invention is prepared by polymerizing a compound (2) with a non-crosslinkable or crosslinkable vinyl monomer or a mixture thereof and using a usual polymerization method such as solution polymerization, solid phase polymerization, bulk polymerization, emulsion polymerization or suspension polymerization. However, it is preferable to employ a solution polymerization method. The solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, for example, water, methanol, ethanol, a protic solvent such as propanol, ether, tetrahydrofuran, ether solvents such as dioxane, Halogenated hydrocarbons such as chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene and toluene; nitrile solvents such as acetonitrile and propionitrile; dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and dimethyl sulfoxide Aprotic polar solvents can be indicated.

As the non-crosslinkable vinyl monomer, for example,
Styrene, p-methylstyrene, p-bromostyrene,
Polymerizable aromatic compounds such as p-chlorostyrene, α-chlorostyrene, α-bromostyrene; acrylic acid, methyl acrylate, ethyl acrylate, lauryl acrylate,
α-methyl chloroacrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate,
Polymerizable carboxylic esters such as propyl methacrylate, butyl methacrylate, and lauryl methacrylate and salts thereof; vinyl ester monomers such as vinyl acetate, vinyl trifluoroacetate, vinyl butyrate, and vinyl benzoate; vinyl chloride, vinyl fluoride, Vinyl halide monomers such as vinylidene chloride and vinylidene fluoride; vinyl ether monomers such as isobutyl vinyl ether and n-butyl vinyl ether; acrylamide, N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide Acrylonitrile, methacrylonitrile, α-
Polymerizable nitriles such as chloroacrylonitrile and vinylidene cyanide; olefin monomers such as ethylene, propylene, isobutylene, pentene, hexene, cyclohexene, norbornene, arene, butadiene, isoprene, chloroprene; vinyl sulfide monomers such as alkyl vinyl sulfide; N-vinyl carbazole, 4
-Nitrogen-containing heterocyclic monomers such as vinyl pyridine and N-vinyl pyrrolidone; vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone; maleic acid, maleic anhydride, acrolein, acrylic acid chloride, vinyl isocyanate, vinyl silane and allyl silane And the like.

Examples of the crosslinkable vinyl monomer include divinylbenzene and divinylnaphthalene. These monomers can be used alone or in combination of two or more.

The charged molar ratio of the compound of the formula (2) of the present invention and the monomer copolymerizable therewith is usually about 0.001 to 99.0: 99.999 to 1.0, preferably 1 to 9.
50: about 99 to 50 is preferable.

This polymerization reaction can usually be carried out more efficiently by adding a polymerization initiator. As the polymerization initiator used at this time, azobisisobutyronitrile, azobis- (2,
Azo-based initiators such as 4-dimethyl) valeronitrile, peroxides such as hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammonium persulfate and potassium persulfate; Examples thereof include redox initiators, phenylmagnesium bromide, and organometallic compounds such as butyllithium, which are obtained by combining ammonium sulfate with, for example, sodium sulfite or divalent iron ions. The amount of these polymerization initiators varies depending on the type, polymerization type and desired molecular weight of the copolymer, but is usually 1 × 10 ^{−5 to} 0.5 mol / mol.
l, preferably 1 × 10 ^{−4 to} 5 × 10 ⁻² mol / l.

The solvent used in the case of employing the solution polymerization method is not particularly limited as long as it does not adversely affect the reaction. Examples of the solvent include water, methanol, ethanol, propanol, methyl cellosolve and ethyl cellosolve. Protic solvents, ether solvents such as ether, tetrahydrofuran, dioxane, dimethoxyethane and diglyme; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene and xylene; acetonitrile and propio Nitrile solvents such as nitrile, dimethylformamide,
Aprotic polar solvents such as dimethylacetamide, hexamethylphosphoric triamide, dimethylsulfoxide and the like can be mentioned. These solvents can be used as a mixture of two or more components.

The reaction temperature and the reaction time vary depending on the reactivity of the monomer and the kind of the solvent used, but are usually from 0 to 100 ° C.
It is preferable to select within the range of ~ 120 hours.

The resulting copolymer can be isolated and purified by a usual post-treatment method. For example, the reaction mixture is poured into an excess solvent in which the product is hardly soluble to precipitate out, and separated by filtration or the like. Can be isolated. If further purification is necessary, it is advisable to employ conventional means such as reprecipitation.

The number average molecular weight Mn of the copolymer of the present invention is 2,0
00-1,000,000, preferably 5,000-500,000, Mw / Mn
= 1.1 to 2.0 (Mw is a weight average molecular weight). The polymerization degree is the raw material concentration in the polymerization reaction, the type and concentration of the initiator,
Since it is determined by factors such as reaction temperature and reaction time, a copolymer having a desired molecular weight and polydispersity can be obtained by selecting these factors according to circumstances.

The obtained copolymer is subjected to ion exchange according to a known method, and the counter anion is changed to one of chloride ion, bromine ion, iodine ion, nitrate ion, perchlorate ion, acetate ion, methyl sulfate ion and the like. It can be a divalent anion such as a valent anion, a sulfate ion or a methyl phosphate ion.

In using the polymer of the present invention, one or more of the above-mentioned polymers as active ingredients can be used in combination.

The polymer of the present invention can be in the form of powder, granule, fiber, film, etc., depending on the method for producing the polymer.

When the polymer of the present invention is used, for example, as an active ingredient of an antibacterial composition, its use is as tap water, cooling water,
Slime control, pools, fishing nets, ship bottoms, underwater structures, food packaging, construction materials, agricultural materials, medical supplies, oral materials (toothbrushes, toothpastes, etc.), eyeglass frames, cosmetics,
There is a wide range of clothing and household goods.

In using the above antibacterial polymer, a known method can be used. For example, when the surface of an object is subjected to antibacterial treatment, one or more of the above polymers can be dissolved in an appropriate solvent and treated by a dipping method or a spray method. In that case, it can be mixed with a known polymer.

The object to which the antibacterial polymer can be used is, specifically, any form of synthetic polymer,
For example, polypropylene, polyethylene, polystyrene,
Polyester, polyamide, polyacrylate, polyurethane, polyvinyl chloride and other natural polymers, such as cottone, wool, feathers, hemp, silk, paper, rubber, etc.
Further, wood, glass, metal, ceramic products and the like can be mentioned.

The form of these objects may be a molded product or a raw material. For example, the antibacterial treatment can be performed in the form of a thread, fiber, film, sheet, granule, powder, or the like.

The polymer of the present invention can provide these substances with high safety and excellent antibacterial activity over a long period of time.

When using an antimicrobial polymer, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide are generally used. , Dimethyl sulfoxide, or a mixture of these solvents with acetone, tetrahydrofuran, benzene, toluene, xylene, or the like. Dissolve so that the concentration becomes 0.01 to 2.0% by weight, preferably 0.1 to 1.0% by weight. The substance to be imparted with antibacterial properties is immersed in the solution, or the solution is applied to the surface by spraying the substance, and then dried to remove the solvent. The drying temperature is from 0 to 80 ° C, preferably
It is desirable to dry at 20-60 ° C in a drying room for 10-48 hours.

Further, the antibacterial polymer has excellent antifouling property in water. In order to use the antibacterial polymer for antifouling in water, the antibacterial polymer can be mixed with a known film-forming composition. At this time, a substance containing a known antifouling component can be added.

When the antibacterial polymer is used for antifouling underwater, it can be specifically used for, for example, fishing nets, ship bottoms, cooling water piping, buoys, dam gates, water tanks such as aquaculture facilities, and underwater structures. It has an excellent effect of preventing adhesion of Aonori, Hiraaonori, Aosanori, barnacles and the like.

When the antibacterial polymer is used for antifouling in water, the solvent is generally methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, N, N-dimethylformamide, dimethylsulfoxide. Or a mixed solvent system of these solvents and benzene, toluene, xylene or the like. Known methods can be used.

The known antifouling component-containing substance which can be used by mixing with the antibacterial polymer is not particularly limited, and examples thereof include a copper compound, a dithiocarbamate compound, a phenylsazine compound and a quaternary compound. Examples thereof include ammonium salt compounds. Further, a cross-linking agent having an antifouling activity, a filler, a monomer, a polymer and the like can be mixed and used.

The coating film-forming composition which can be mixed with the antibacterial polymer may be any known one, for example, acrylic acid resin, phthalic acid resin and aminoalkyd resin. And synthetic resin emulsions and lacquers.

[0078]

The present invention will be described in detail below with reference to examples.

Example 1 23.1 g (0.16 mol) of N, N, N ', N'-tetramethyl-1,4-diaminobutane (hereinafter abbreviated as TMB) was dissolved in 50 ml of acetonitrile, and stirred at room temperature under stirring with lauryl bromide. 10.0 g (0.04 mol) was added dropwise, followed by heating at 70 ° C. for 3 hours. Next, the reaction solution was cooled to room temperature, and the resulting white precipitate was filtered to give N, N, N ′, N′-tetramethyl-1,4.
-Diaminobutane-N, N'-dilauryldibromide
0.12g was produced as a by-product (by-product rate: 1.0%). The filtrate was concentrated under reduced pressure and most of the TMB was distilled off. The white paste-like residue generated was washed with 40 ml of hexane, and the hexane layer was separated by decantation to obtain a white wax-like substance from which unreacted TMB had been completely removed. Obtained. When thoroughly dried under reduced pressure This material with vacuum pump N, N, N ', N'- tetramethyl-1,4-diaminobutane -N- lauryl bromide (hereinafter abbreviated as TML-C ₄₎ was produced 14.5g (Yield 92
%). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.83 (t, 3H, CH)
_{3), 1.19~1.29 (m, 20H} , CH 2), 1.60~2.00
_{(M, 6H, CH 2)} , 2.68 (s, 6H, CH 3 -N),
_{3.05 (s, 6H, CH 3} -N), 3.15~3.28 (m, 2
_{H, CH 2 N), 3.37~3.45} (m, 2H, CH 2 N)

Examples 2 to 5 Instead of TMB, 20.8 g of N, N, N ', N'-tetramethyl-1,3-diaminopropane (hereinafter abbreviated as TMP)
(0.16 mol), N, N, N ', N'-tetramethyl-1,6-diaminohexane (hereinafter abbreviated as TMH) 27.5 g (0.16 mol), N, N, N', N'-tetramethyl- 36.5 g (0.16 mol) of 1,10-diaminodecane (hereinafter abbreviated as TMD) or N,
Except that 36.5 g (0.16 mol) of N, N ', N'-tetraethyl-1,6-diaminohexane (hereinafter abbreviated as TEH) was used, the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain the desired products. A monoquaternary ammonium salt derivative was obtained. At this time, a small amount of a bisquaternary ammonium salt derivative was by-produced. Table 1 shows the results. In the table, Et represents an ethyl group.

Examples 6 and 7 27.5 g (0.16 mol) of TMH was used in place of TMB, and 8.8 g of decyl bromide was used in place of lauryl bromide.
g (0.04 mol) or 13.3 g of octadecyl bromide (0.
The same reaction and post-treatment as in Example 1 were carried out, except that the compound (04 mol) was used to obtain the desired monoquaternary ammonium salt derivative. At this time, a small amount of a bisquaternary ammonium salt derivative was by-produced. The results are shown in Table 1.

[0082]

[Table 1]

Example 8 11.1 g (26.4 mmol) of TML-C ₆ obtained in Example 3 was dissolved in 200 ml of acetone, and 3.7 g (24 mmol) of 4-chloromethylstyrene was added dropwise with stirring at room temperature. Then 5
When heated at 0 ° C. for 17 hours, white crystals precipitated. The reaction solution was cooled to room temperature, and the resulting white crystals were isolated by filtration, washed with cold acetone, and dried. N, N, N ', N'-tetramethyl-N-lauryl-N'-(4-vinyl) benzyl Hexamethylene diammonium bromide chloride (T
Abbreviated as MLS-C ₆₎ was produced 12.0 g (yield: 87
%). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.86 (t, 3H, CH
_{3), 1.92~1.37 (m, 18H} , CH 2), 1.53~1.73
_{(M, 6H, CH 2)} , 1.98~2.21 (m, 4H, C
_{H 2), 3.26 (s,} 6H, CH 3 N), 3.37 (s, 6H,
_{CH 3 N), 3.40~3.50 (m} , 2H, CH 2 N), 3.68~
3.87 (m, 4H, CH ₂ N), 4.95 (s, 2H, CH ₂ A)
r), 5.38 (d, 1H, vinyl), 5.81 (d, 1H, viny)
l), 6.71 (dd, 1H, vinyl), 7.46 (d, 2H, Ar)
H), 7.62 (d, 2H, ArH)

Examples 9 to 12 Allyl bromides were used in place of 4-chloromethylstyrene.
2.90 g (24 mmol), 4-bromo-1-butene 3.24 g
(24 mmol), 3.58 g of bromomethyl vinyl ketone (24
Mmol) or 6.79 g (24 mmol) of N-2-tosyloxyethyl acrylamide, and reacted and worked up in the same manner as in Example 8 except that acetone or ethyl acetate was used as a solvent. An ammonium salt derivative was obtained. Table 2 shows the results.

[0085]

[Table 2]

[0086] Each TML-C ₃ 9.09g (24 mmol) in place of Example _{13~18 TML-C 6, TML-} C 4 9.43g (24 mmol), TML
-C ₁₀ 12.4 g (26 mmol), TMD-C ₆ 10.2 g (26
_{Mmol), TMO-C 6 13.1g (} 26 mmol) or T
Each other using the EL-C ₆ 12.4g (26 mmol) is then substantially the same reaction and after-treatment as in Example 8 to give the bis-quaternary ammonium salt derivative of interest. Table 3 shows the results.

[0087]

[Table 3]

[0088] Example 19 Example 3 obtained in TML-C ₆ 8.42 g (20 mmol) thereto at room temperature was dissolved in methanol 200 ml 3- bromo-l
2.78 g (20 mmol) of propanol were added. Next, the mixture was heated to 50 ° C. and reacted for 12 hours, and then concentrated under reduced pressure to obtain 11.1 g of a white solid residue. This was poured into 100 ml of ethyl acetate, washed, filtered, the solution layer was removed and dried to obtain N, N, N ', N'-tetramethyl-N-.
(3-hydroxy) propyl -N'- lauryl hexamethylene diammonium dibromide (TMLP-C ₆₎
Was obtained as white crystals (yield 89%). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.87 (t, 3H, C
_{H 3), 1.20~1.57 (m,} 26H, CH 2), 1.63~1.80
_{(M, 4H, CH 2)} , 3.25 (t, 2H, CH 2 O), 3.
39 (s, 6H, CH ₃ N), 3.50 (s, 6H, CH
_{3 N), 3.45~3.59 (m,} 8H, CH 2 N)

Example 20 The reaction and after-treatment were carried out in substantially the same manner as in Example 19 except that 4.88 g (20 mmol) of 4-tosyloxy-1-butanol was used instead of 3-bromo-1-propanol. N,
N ', to give 10.2 g N'-tetramethyl -N- (4- hydroxy) butyl -N'- lauryl hexamethylene diammonium bromide toluenesulfonate (TMLB-C ₆₎ as white crystals (91% yield). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.87 (t, 3H, C
_{H 3), 1.20~1.56 (m,} 30H, CH 2), 1.63~1.82
(M, 4H, CH ₂ ), 2.25 (s, 3H, CH ₃ Ar),
3.39 (s, 6H, CH ₃ N), 3.49 (s, 6H, CH
_{3 N), 3.35~3.63 (m,} 8H, CH 2 N), 7.55 (d,
2H, ArH), 7.86 (d, 2H, ArH)

[0090] was added thereto 2-bromoethyl acetate 6.67 g (40 mmol) 16.8 g TML-C ₆ obtained in Example 21 Example 3 (40 mmol) at room temperature was dissolved in acetone 200 ml. Mix the mixture at 50 ° C for 12
The white crystals formed after the reaction for hours were isolated by filtration.
23.1 g of N, N ', N'-tetramethyl-N- (2-acetoxy) ethyl-N'-laurylhexamethylenediammonium dibromide were obtained. This was dissolved in 120 ml of 2% dilute hydrobromic acid, stirred at 60 ° C. for 15 hours, and then the mixture was concentrated under reduced pressure. The obtained pale yellow wax was put into ethyl acetate, washed, filtered, the solution layer was removed, and dried to obtain N, N, N ', N'-tetramethyl-N- (2- hydroxy) ethyl -N'- lauryl hexamethylene diammonium dibromide (abbreviated as TMLE-C ₆₎ was obtained 17.9g as almost white crystals (82% yield). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.86 (t, 3H, C
_{H 3), 1.22~1.56 (m,} 24H, CH 2), 1.63~1.79
_{(M, 4H, CH 2)} , 3.26 (t, 2H, CH 2 O), 3.
40 (s, 6H, CH ₃ N), 3.51 (s, 6H, CH
_{3 N), 3.46~3.60 (m,} 8H, CH 2 N)

Example 22 5.46 g (10 mmol) of TMLE-C ₆ obtained in Example 21
And 1.45 g (12 mmol) of allyl bromide in dichloromethane 5
0 ml and triethylamine 1.01 g (1
0 mmol) was added dropwise. After the mixture was stirred at 40 ° C. for 15 hours, it was cooled to room temperature and the resulting white precipitate was removed by filtration. The filtrate was concentrated to give a pale yellow wax. This is thoroughly washed with acetone and dried to obtain N,
N, N ', N'-tetramethyl-N- (2-allyloxy)
Ethyl -N'- lauryl hexamethylene diammonium dibromide (TML2A-C ₆₎ was obtained 4.2g as a nearly white crystals (72% yield). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.86 (t, 3H, C
_{H 3), 1.22~1.57 (m,} 24H, CH 2), 1.63~1.80
_{(M, 4H, CH 2)} , 3.12 (d, 2H, CH 2 O), 3.
26 (t, 2H, CH ₂ O), 3.40 (s, 6H, CH
_{3 N), 3.52 (s,} 6H, CH 3 N), 3.45~3.60 (m,
8H, CH ₂ N), 5.39 (d, 1H, vinyl), 5.68
(M, 1H, vinyl), 5.92 (d, 1H, vinyl)

Example 23 3.44 g (6 mmol) of TMLS-C ₆ and 5.62 g of styrene
(54 mmol) was dissolved in 10 ml of methanol.
A solution prepared by dissolving 50 mg (0.3 mmol) of BN in 2 ml of methanol was added. The mixture was stirred under a nitrogen atmosphere at 65 ° C. for 22 hours, resulting in a viscous solution. The reaction solution was poured into water to terminate the polymerization reaction, and the resulting white polymer was isolated by filtration and dried under reduced pressure to obtain a white polymer. The procedure of re-dissolving in methanol and throwing it into water was repeated twice to purify and dry to obtain 6.3 g of a white powdery polymer. The white powder was analyzed by TLC, IR and ¹ H-NMR analyses.
It was confirmed to be a copolymer of MLS-C ₆ and styrene. This is dissolved in dimethylformamide as a solvent and
According to PC analysis (based on polystyrene), it was found that Mn was 158,000 and the polydispersity index Mw / Mn was 1.4. By determining the content of quaternary ammonium groups by a colloid titration method using polyvinyl potassium sulfate (PVSK), TMLS-
The copolymer composition of C ₆ and styrene was confirmed to be 13:87.

[0093] The same reaction and after-treatment other was replaced with Example 24 TMLS-C ₆ to TMLV-C ₃ 3.19g (6 mmol) of Example 23 to give the means pursuant white powder polymer 5.9 g. The white polymer is TLC,
From IR and ¹ H-NMR analyses, it was confirmed that the copolymer was a copolymer of TMLV-C ₃ and styrene.

Similarly, GPC analysis revealed that Mn was 86,000 and the polydispersity index Mw / Mn was 1.8. By determining the quaternary ammonium group content by a colloid titration method, TML is determined.
Copolymerization composition of the V-C ₃ and styrene was found to be nine ninety-one.

[0095] The reaction and treatment in the same manner as in Example 25~26 TMLS-C ₆ a TMLV-C ₄ 3.26g (6 mmol) or TMLV-C ₁₀ except that instead of 3.78 g (6 mmol) of Example 23 This gave 6.3 g and 6.4 g of a white powdery polymer, respectively. These polymers are TL
From C, IR and ¹ H-NMR analyses, TMLV-
It was confirmed to be a copolymer of a C ₄ or TMLV-C ₁₀ and styrene.

[0096] Results having conducted the GPC and colloidal titration in the same manner as in Example 23, those from TMLV-C ₄ Mn = 17.2
Ten thousand, polydispersity Mw / Mn = 2.0, the copolymer composition of the TMLV-C ₄ and styrene Atsuta in eighty-four past four p.m.. TMLV-C ₁₀
From Mn = 62,000, polydispersity Mw / Mn = 2.2, T
Copolymerization composition of the MLV-C ₁₀ and the styrene was found to be seven ninety-three.

[0097] The same reaction and after-treatment as in Example 27~28 TMLS-C ₆ a TMDV-C ₆ 3.27g ₍₆ mmol) or TMOV-C ₆ except that instead of 3.95 g (6 mmol) of Example 23 This gave 6.6 g and 6.4 g of a white powdery polymer, respectively. These polymers are TL
From C, IR and ¹ H-NMR analyses, TMDV-
It was confirmed to be a copolymer of a C ₆ or TMOV-C _6.

[0098] Results having conducted the GPC and colloidal titration in the same manner as in Example 23, those from TMDV-C ₆ Mn = 12.4
Ten thousand, polydispersity Mw / Mn = 2.0, the copolymer composition of the TMDV-C ₆ and styrene Atsuta in eighty-two past six p.m.. In addition, TMOV-C ₆
Are from Mn = 81,000, polydispersity Mw / Mn = 1.9, T
Copolymerization composition of the MOV-C ₆ and styrene was found to be nine ninety-one.

Example 29 6.88 g (12 mmol) of TMLS-C ₆ and 11.2 g of styrene
(108 mmol) was dissolved in 12 ml of methanol.
A solution of 32 mg (0.19 mmol) of BN dissolved in 1 ml of methanol was added. The mixture was stirred at 65 ° C. under a nitrogen atmosphere for 39 hours, resulting in a viscous solution. Post-treatment was conducted in substantially the same manner as in Example 23 to obtain 13.7 g of a white powdery polymer. The white polymer was analyzed by TLC, IR and ¹ H-NMR analysis to obtain TMLS-
It was confirmed to be a copolymer of a C ₆ and styrene.

Similarly, GPC analysis revealed that Mn = 480,000, possibly
The dispersion Mw / Mn was 1.9. By colloid titration
By determining the quaternary ammonium group content, the TML
SC ₆The copolymer composition of styrene and styrene was 10:90.

Example 30 6.88 g (12 mmol) of TMLS-C ₆ and 1.25 g of styrene
(12 mmol) was dissolved in 4 ml of methanol.
A solution prepared by dissolving 20 mg (0.12 mmol) of BN in 1 ml of methanol was added. The reaction and after-treatment were carried out in substantially the same manner as in Example 23 to obtain 6.5 g of a white polymer. The white polymer is TL
From C, IR and ¹ H-NMR analyses, it was confirmed that the copolymer was a copolymer of TMLS-C ₆ and styrene.

When this was subjected to GPC analysis, Mn = 200,000,
The polydispersity Mw / Mn was 1.6. By determining the quaternary ammonium group content by a colloid titration method, T
Copolymerization composition of the MLS-C ₆ and styrene was confirmed and 64:36.

Example 31 The reaction and post-treatment were carried out in substantially the same manner as in Example 23 except that styrene was replaced by 5.40 g (54 mmol) of methyl methacrylate to obtain 6.1 g of a white polymer. This is TLC, IR
And ¹ H-NMR analysis confirmed that the copolymer was a copolymer of TMLS-C ₆ and methyl methacrylate.
16:84.

This was subjected to GPC in the same manner as in Example 23.
As a result of the analysis, Mn was 104,000 and the polydispersity Mw / Mn was 1.4.

Example 32 A reaction was conducted in the same manner as in Example 23 except that 3.89 g (54 mmol) of acrylic acid was used instead of styrene. The reaction mixture was poured into ether to terminate the polymerization reaction, and the resulting white precipitate was isolated by filtration and dried to obtain a white powdery polymer 5.8.
g was obtained. This compound TLC, confirms the copolymer of TMLS-C ₆ and acrylic acid from IR and ¹ H-NMR analysis, the copolymerization composition of both Atsuta almost seven ninety-three.

This was subjected to GPC in the same manner as in Example 23.
As a result of analysis, it was found that Mn = 866,000 and polydispersity Mw / Mn = 1.9.

Example 33: 3.44 g (6 mmol) of TMLS-C _{6 and} 8.52 g (60 mmol) of a 50% aqueous acrylamide solution were dissolved in 10 ml of water.
To this was added 50 mg of 2,2'-azobis (2-amidopropane) dihydrochloride dissolved in 2 ml of water to obtain a homogeneous solution.
When the reaction was carried out at 50 ° C. for 2 hours under nitrogen replacement, the reaction solution gelled. This was poured into an excess of dioxane to terminate the polymerization reaction, and the resulting white polymer was isolated by filtration and dried under reduced pressure to obtain 7.0 g of a white polymer. This compound was confirmed TLC, a copolymer of TMLS-C ₆ and acrylamide from IR and ¹ H-NMR analysis.

GPC analysis and colloid titration were carried out in the same manner as in Example 23, whereby Mn = 328,000 and the polydispersity Mw /
Mn = 1.9, the copolymer composition of the TMLS-C ₆ and acrylamide Atsuta in eight ninety-two.

Example 34 2.87 g (5 mmol) of TMLS-C ₆ and 4.30 of vinyl acetate
g (50 mmol) was dissolved in 7 ml of dry DMF.
A solution prepared by dissolving 41 mg (0.25 mmol) of IBN in 1 ml of DMF was added. The mixture was stirred at 60 ° C. for 20 hours under a nitrogen atmosphere to give a viscous solution. The reaction solution was poured into ether to terminate the polymerization reaction, and the resulting white polymer was isolated by filtration and dried under reduced pressure to obtain 4.6 g of a white powder. This is TL
From C, IR and ¹ H-NMR analyses, the copolymer was confirmed to be a copolymer of TMLS-C ₆ and vinyl acetate. By GPC analysis in the same manner as in Example 23, Mn = 73,000, polydispersity M
w / Mn = 1.6. When quantifying the content of quaternary ammonium groups by colloid titration copolymer composition of TMLS-C ₆ and vinyl acetate Atsuta in eighty-one past seven p.m..

Example 35 The same procedure as in Example 34 was carried out except that vinyl acetate was replaced by 2.65 g (50 mmol) of acrylonitrile, to obtain 3.2 g of a white powdery polymer. This is TLC, IR
From ¹ H-NMR analysis, the copolymer was confirmed to be a copolymer of TMLS-C ₆ and acrylonitrile. As a result of GPC analysis, Mn
= 51,000 and polydispersity index Mw / Mn = 2.2. When the content of quaternary ammonium groups is determined by the colloid titration method,
Copolymerization composition of the MLS-C ₆ and acrylonitrile 17: 8
It was three.

Example 36 2.87 g (5 mmol) of TMLS-C _{6 and} 5.21 g of styrene
(50 mmol) and 0.65 g (5 mmol) of divinylbenzene were dissolved in 20 ml of methanol, and 50 mg of AIBN was added thereto.
(0.3 mmol) in 2 ml of methanol was added. The mixture gelled when stirred at 60 ° C. for 19 hours under a nitrogen atmosphere. The reaction solution was poured into water to isolate a white rubbery polymer produced and dried under reduced pressure to obtain a white polymer. This was washed under reflux in methanol, and a methanol solution containing the swollen polymer was poured into cold methanol. The precipitated white polymer was isolated by filtration and dried under reduced pressure to obtain 7.0 g of a white polymer. Although the polymer was poorly soluble in most solvents, TLC, IR and ¹ H-NMR (thermal DMSO-
d ₆ ) From the analysis, it was confirmed that the copolymer was a crosslinked copolymer produced from TMLS-C ₆ , styrene and divinylbenzene. From elemental analysis, the content of quaternary ammonium groups was 1.25 millieq / g.

Example 37 TMLS-C ₆ was converted to 3.25 g (6 mmol) of TMLA-C ₆
In addition, AIBN is replaced with 2,2'-bis (N-phenylamidinyl)
The reaction and post-treatment were carried out in the same manner as in Example 23 except that -2,2'-azopropane dihydrochloride was changed to 40 mg to give a white polymer 4.9.
g was obtained. The white polymer was obtained by TLC, IR and ¹ H-NMR.
It was confirmed copolymer of TMLA-C ₆ and styrene from the analysis. According to GPC analysis, Mn = 42,000, polydispersity Mw / Mn
= 2.2. Copolymerization composition of the TMLA-C ₆ and styrene by quantifying the content of quaternary ammonium groups by the colloid titration method is 0.5: Atsuta 99.5.

[0113] Example _{38 TMLS-C 6 TMLB-C} 6 3.33g (6 mmol)
In addition, AIBN is replaced with 2,2'-bis (N-phenylamidinyl)
The reaction and post-treatment were carried out in the same manner as in Example 23 except that -2,2'-azopropane dihydrochloride was changed to 40 mg to give a white polymer 5.2
g was obtained. This compound was confirmed TLC, a copolymer of TMLB-C ₆ and styrene from IR and ¹ H-NMR analysis. From GPC analysis, Mn = 48,000, polydispersity Mw / Mn =
2.4. Copolymerization composition of the TMLB-C ₆ and styrene by quantifying the content of quaternary ammonium groups by colloid titration was found to be one ninety-nine.

[0114] The same reaction and after-treatment as in Example 39 TMLS-C ₆ a TMLK-C ₆ except that instead of 3.42 g (6 mmol) of Example 23 to give the means pursuant white polymer 4.4 g. These are TLC, IR and ¹
H-NMR analysis confirmed that the copolymer was a copolymer of TMLK-C ₆ and styrene. Similarly, from GPC analysis and colloid titration, Mn = 101,000, polydispersity Mw / Mn = 1.8,
Copolymer composition of TMLK-C ₆ and styrene Atsuta 5:95.

[0115] The same reaction and after-treatment other was replaced with Example 40 TMLS-C ₆ to TMLC-C ₆ 4.22g ₍₆ mmol) of Example 23 to give the means pursuant white polymer 4.6 g. These are TLC, IR and ¹
H-NMR analysis confirmed that the copolymer was a copolymer of TMLC-C ₆ and styrene. Similarly, GPC analysis and colloid titration revealed that Mn = 90,000 and polydispersity Mw / Mn = 1.
7, the copolymerization composition of the TMLC-C ₆ and styrene Atsuta in six ninety-four.

[0116] The same reaction and after-treatment other was replaced with Example 41 TMLS-C ₆ to TELV-C ₆ 3.78g ₍₆ mmol) of Example 23 to give the means pursuant white polymer 7.0 g. These are TLC, IR and ¹
1 H-NMR analysis confirmed that the copolymer was a copolymer of TMLV-C ₆ and styrene. Similarly, as a result of GPC analysis and colloid titration, Mn = 14,000, and polydispersity Mw / Mn =
1.9, the copolymer composition of the TELV-C ₆ and styrene twelve eighty-eight
It was.

Comparative Example 1 In a reaction for obtaining a copolymer from styrene (abbreviated as ST) and 4-chloromethylstyrene (abbreviated as CS) by a conventional solution polymerization, 77.0 g (0.74 mol) of styrene and 4-chloromethyl 9.2 g (0.06 mol) of styrene in tetrahydrofuran
In the presence of 0.66 g (4 mmol) of AIBN in 40 ml
The reaction was performed at 20 ° C. for 20 hours. The mixture was poured into THF / methanol, purified by reprecipitation, filtered, isolated and dried in vacuo to obtain 73.3 g of a white powdery polymer (abbreviated as PCS). The polymer was identified as a two-component copolymer from TLC, ¹ H-NMR, GPC analysis and the like.

As a result of quantitative analysis of all halogens and elemental analysis by an oxygen flask combustion method, the composition of ST and CS in PCS was 91.7: 8.3 in molar ratio. GPC measurement (in terms of polystyrene) using THF as a solvent showed that the PCS had a number average molecular weight Mn of 134,000 and a polydispersity Mw / Mn of 1.57.

Next, 19.6 g of the PCS obtained here was added to THF 500
It was dissolved in ml TML-C ₄ 7.07g obtained in Example 1 to (1
8 mmol) and reacted at 80 ° C. for 21 hours. The reaction mixture was cooled to room temperature and then poured into water, and the precipitate was filtered and dried to obtain a white polymer. This was dissolved in methanol, further purified twice by reprecipitation in water, and then dried to obtain 23.4 g of a white powdery polymer. This compound TLC, ¹ H
TML-C ₄ to result PCS analyzed by like -NMR was confirmed that it was the desired product which has been introduced.

Determination of the total halogen content of the polymer by the oxygen flask combustion method, determination of the ionic halogen content by the silver nitrate titration method, determination of the content of N% by the elemental analysis method and quaternary ammonium group content by the colloid titration method gave the ST unit content. , the content of the residual chloromethyl groups i.e. unreacted CS Yunitsuto and TML-C ₄ was calculated Yunitsuto supported amount of these compositions are respectively 91.7 mole%, Atsuta 0.5 mole% and 7.8 mole%.

Comparative Test Example 1 The polymers obtained in Example 25 and Comparative Example 1 were each placed in a glass container. These were allowed to stand in a constant-temperature bath controlled at 50 ° C. under light-shielding conditions, and changes over time were observed. After one week, no change was observed in the polymer of Example 25, whereas the polymer obtained in Comparative Example 1 was slightly yellow and produced an acidic gas which turned the pH test paper red. Similarly, after 20 days, the one obtained in Example 25 had no change in appearance and good solubility in methanol, whereas the one obtained in Comparative Example 1 was mostly transformed into a component insoluble in methanol. Was.

Test Example 1 Preparation of Antibacterial Finished Fabric The compound synthesized in Example 23 was used as a test compound, and this compound was dissolved in methanol to prepare 0.1, 0.2, and 0.5 wt% methanol solutions. Next, cotton kanakin and a JIS standard cloth (hereinafter abbreviated as cloth) were immersed in the above methanol solution, and the solution was impregnated (padding method). Then, immediately measure the weight, cure at 105 ° C for 30 minutes, and fully adhere the test compound to the cloth.
Was used in the following tests.

The weight (mg / g cloth) of the test compound fixed to the antibacterial cloth is represented by the following formula [I]. C = (BA) (W / 100) (1 / A) (1000) ... [I] A: Weight of the first cloth (g / constant area) B: Weight of the cloth immediately before clearing (g / constant) Area) C: Weight of the test compound fixed on the antibacterial cloth (mg / g)
Cloth) W: Concentration of methanol solution of test compound (wt%)

According to the above equation [I], the relationship between the W value and the C value is as follows. W: (Methanol of test compound C: (Concentration of solution fixed to antibacterial cloth) Weight of test compound) (wt%) (mg / g cloth) 0.1 1.0 0.2 2.0 0.5 5.0

Antibacterial activity test The “antibacterial processed cloth” obtained as described above was used in accordance with the “Test Method for Inhibiting Bacterial Growth of Textile Products Treated with Antibacterial Process” (hereinafter referred to as the “Antibacterial Fiber Test Method”). Abbreviated). The test bacteria were Pseudomonas aeruginosa
Add ATCC 10145 and add Staphylococcus aureus F
DA 209P, Bacillus subtilis ATCC 6633, Kl
ebsiella pneumoniae ATCC 4352, Escherichia c
oli IFO 3301, Pseudomonas aeruginosa ATC
Five strains of C10145 were used. The method for measuring the number of viable bacteria is described in the Japan Society of Antimicrobial and Antifungal Processes, Handbook of Antimicrobial and Antifungal Products, 1986, p. 678-69.
I referred to 1.

Display of the results The display of the test results was as follows. N for the number of initial bacteria
(I) N (D)
The bactericidal index was determined from the following formula [II]. Sterilization index = log N (I)-log N (D) ... [II]

Next, this germicidal index is divided into the following four stages, and when the germicidal index is less than 1 ... 1, when the germicidal index is 1 or more and less than 2 ... 2, the germicidal index is 2 or more and less than 3 In the case of ...... 3, and in the case where the bactericidal index is 3 or more ... 4, the results are shown in Table 4.

[0128]

[Table 4]

[0129]

According to the present invention, an antibacterial polymer having excellent bactericidal activity, high safety and stability, and capable of maintaining its efficacy over a long period of time can be obtained.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Mitsuo Akada 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Inside the Tokushima Research Laboratory, Otsuka Chemical Co., Ltd. (56) References JP-A-64-26610 (JP, A) 5-230149 (JP, A) JP-A-6-56935 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 212/14 C08F 216/14 C08F 226/02

Claims (1)

(57) [Claims] 1. A method for producing a copolymer, comprising copolymerizing a monomer represented by the general formula (2) with a non-crosslinkable or crosslinkable vinyl monomer or a mixture thereof. Embedded image [Wherein, R ¹ represents a hydrogen atom, a methyl group, a chloro group or a cyano group, R ² represents an alkylene group having 1 to 4 carbon atoms, R ³ represents an alkylene group having 3 to 10 carbon atoms, and R ⁴ represents a carbon atom. R ^{5 to} R ⁸ are the same or different and have 1 carbon atom.
And represents an alkyl group of 1 to 3, each of which may contain a substituent. A is a methylene group, which may have a substituent phenylene _{group, -CH 2 O -, - CH} 2 CH 2 O -, - C
^{O -, - CO-N (} R 9) -, indicating the ^{(R 9} represents a hydrogen atom or a methyl group.) Or a vinylene group. m is 0 or 1
Is shown. X and Y are the same or different and represent a monovalent anion, or both represent a divalent anion. ]