JPH0656935A - Homopolymer and its production - Google Patents

Abstract

PURPOSE:To provide an antifungal polymer which has a specified molecular structure, is highly safe and stable, and exhibits an excellent fungicidal action for a long term. CONSTITUTION:This homopolymer comprises repeating structural unit of the formula [wherein R<1> is H, methyl, chloro, or cyano; R<2> is 1-4C alkylene; R<3> is 3-10C alkylene; R<4> is 6-18C alkyl; R<5> to R<8> are each independenly 1-3C alkyl provided that R<1> to R<8> may each be substd.; A is methylene, -CH2O-, -CH2CH2 O-,-CO, -CON(R<9>)- (wherein R<9> is H or methyl), or vinylene; m is 0 or 1; and X and Y are each independently a monovalent anion or they are united to represent a divalent anion].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer and a method for producing the same. According to the present invention, there is provided an antibacterial polymer having excellent bactericidal activity, high safety and stability, and capable of maintaining its efficacy over a long period of time.

The antibacterial polymer of the present invention is, for example,
Sterilization of cooling water, pool water, etc., antifouling composition for slime control and fishing nets, ship bottoms, underwater structures, food packaging materials, building materials, agricultural materials, medical products, oral materials (toothbrush, toothpaste, etc.) , Eyeglass frames, cosmetics, clothing,
It can be used for a wide range of purposes such as household items.

[0003]

2. Description of the Related Art Among conventional antibacterial compounds, those having a low molecular weight are simply mixed with materials (eg, resins) constituting various kinds of products, and therefore, the antibacterial compounds cannot be exposed to the outside. Elution and accompanying reduction in antibacterial activity are unavoidable, and further, toxicity to the living body in contact with the product becomes a problem.

In order to solve these problems, the development of polymers having antibacterial properties is under way. Known antibacterial polymers include, for example, those having a repeating unit represented by the general formula [Chemical Formula 3] (JP-A-61-100254), and those having a repeating unit represented by the general formula [Chemical Formula 4]. (Japanese Patent Laid-Open No. 61-246205) and the like are known.

[0005]

[Chemical 3]

[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]

[Chemical 4]

[In the formula, 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 sufficiently satisfactory in their antibacterial activity.

Further, the above-mentioned antibacterial polymer is produced by reacting a polymer having a reactive chloro group in a side chain with a tertiary amine and substituting the tertiary amine for the reactive chloro group. It is difficult to perform the substitution completely, and accordingly, many active functional groups containing chlorine atoms remain in the molecule, so that the antibacterial polymer itself is stable and safe to humans. There's a problem.

In order to solve such a problem, it is also practiced to synthesize an antibacterial polymerizable monomer and copolymerize it with another monomer to produce an antibacterial polymer. For example, an antifouling paint containing a copolymer containing a monomer represented by the general formula [Chemical Formula 5] as an active ingredient is also known (JP-A-2-64167).

[0012]

[Chemical 5]

[Wherein R ¹⁴ represents a linear or branched alkyl group 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 a report by Senuma et al., Chloromethylstyrene and cetyldimethylamine [C ₁₆ H ₃₃ N (C
H ₃ ) ₂ ] to obtain a quaternary ammonium salt monomer represented by the general formula [Chemical formula 6], which is copolymerized with acrylonitrile to obtain a polymer [(Research on fiber polymer materials Tokoro Research Report No. 159 (1988), pp. 17-2
2]. However, these polymers also do not have sufficiently satisfactory antibacterial activity.

[0015]

[Chemical 6]

Further, in US Pat. No. 4,0092,01, a cationic monomer represented by the formula [Chemical Formula 7] is obtained and polymerized to produce a polymer, which is used as an adsorbent. Alternatively, it is only described that it is effective in improving antistatic properties, dye acceptance, etc., and that it is not used for antibacterial purposes is not described at all. In addition, since the above-mentioned monomer has a functional group containing a polymerizable vinyl group and a cationic group bonded via an ester group, it is easily hydrolyzed, and accordingly, in the polymer derived from the cationic monomer, the cationic group ( There is a problem that the side chain containing a diammonium group) is desorbed from the polymer main chain and eluted to lower the function.

[0017]

[Chemical 7]

[0018]

An object of the present invention is to provide an antibacterial polymer having excellent bactericidal activity, high safety and stability, and capable of maintaining its efficacy for a long period of time. It is in.

[0019]

The present invention has the general formula [Chemical formula 1]
The present invention relates to a homopolymer having a repeating unit represented by

[0020]

[Wherein R ¹ is a hydrogen atom, a methyl group, a chloro group or a cyano group, R ² is an alkylene group having 1 to 4 carbon atoms, R ³ is an alkylene group having 3 to 10 carbon atoms, R ⁴ represents an alkyl group having 6 to 18 carbon atoms, and R ^{5 to} R ⁸ are the same or different and represent an alkyl group having 1 to 3 carbon atoms, and each may contain a substituent. A is a methylene _{group, -CH 2 O -, - CH} 2
_{CH 2 O -, - CO -} , - CO-N (R 9) -, indicating the (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 each represents a monovalent anion, or both represent a divalent anion. ]

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

In the above general formula (1), the anion represented by X and Y is not particularly limited as long as it can neutralize the positive charge, and examples thereof include chlorine ion, bromine ion, iodine ion and nitrate ion. , Monochlorinated anions such as perchlorate, acetate, methylsulfate, benzenesulfonate, chlorobenzenesulfonate and toluenesulfonate, and divalent anions such as sulfate and methylphosphate. Can be mentioned.

In the above general formula (2), the group represented by A is a methylene group, --CO--, --CO--N (R ⁹ )-,
(R ⁹ is the same as above.) Or a compound (2a) which is a vinylene group is produced, for example, by reacting a compound represented by the general formula [Chemical formula 8] with a compound represented by the general formula [Chemical formula 9]. it can.

[0024]

[Chemical 8]

[In the formula, R ^{3 to} R ⁸ and X are the same as defined above. ]

[0026]

[Chemical 9]

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

The above reaction is usually carried out in a solvent with heating if necessary. 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. , Halogenated hydrocarbons such as carbon tetrachloride, acetone, ethyl acetate, dimethyl sulfoxide, dimethylformamide and the like. During the reaction, since the target compound (2a) and the compound (9) are both polymerizable, a usual polymerization inhibitor such as hydroquinone or catechol may be added to the reaction system if necessary. The compounding ratio of the compound (8) and the compound (9) is not particularly limited and can be appropriately selected from a wide range, but the compound (9) is usually about 0.7 to 1.2 times mol, preferably 0.9 to 1.0 times the compound (8).
It is sufficient to use about twice the molar amount.

The mono-quaternary ammonium salt derivative of the above general formula (8) is, for example, a lower alkyl group-substituted alkanediamine derivative represented by the general formula [Chemical formula 10].
1] is produced by reacting the compound represented by 1] with or without a solvent in the presence of heat.

[0030]

[Chemical 10]

[In the formula, R ³ and R ^{5 to} R ⁸ are the same as above. ]

[0032]

Embedded image 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 usually the compound (10) is about 1.0 to 5 times mol, preferably 1.2 to about the compound (11).
It may be about 4 times the molar amount.

Specific examples of the compound (10) include N, N, N ', N'-tetramethyl-1,3-propanediamine and 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,
Examples thereof include N, N, N ′, N′-tetraethyl-1,6-hexanediamine. In addition, specific examples of the compound (11) include, for example, alkyl chloride having about 6 to 18 carbon atoms, alkyl bromide, alkyl iodide, benzenesulfonic acid alkyl ester, chlorobenzenesulfonic acid alkyl ester, toluenesulfonic acid alkyl ester and the like. Can be mentioned.

Specific examples of the compound (9) include, for example, allyl halides or methallyl halides whose halogen atom is chlorine, bromine or iodine, allyl benzene sulfonate, allyl benzene sulfonate, allyl toluene sulfonate, chloro. Methylstyrene, chloromethylvinylketone, bromomethylvinylketone, 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-bromoethylmethacrylamide, N-2-tosyloxyethylacrylamide, N-methyl-N-2-tosyloxyethylmethacrylamide, and the like.

Further, in the general formula (2), the compound (2b) in which the group represented by A is —CH ₂ O— or —CH ₂ CH ₂ O— is represented by, for example, the general formula [Chemical Formula 12]. It can be produced by reacting a compound with a compound represented by the general formula [Chemical Formula 13].

[0037]

[Chemical 12]

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

[0039]

[Chemical 13]

[Wherein R ¹ is the same as above. A ² represents a methylene group or an ethylene group. Z is a halogen atom and has 1 carbon atom
A lower alkoxy group having 4 to 4, 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 with heating if necessary. The solvent is not particularly limited as long as it does not affect the reaction, and examples thereof include ether, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, dimethyl sulfoxide and the like. During the reaction, since the target compound (2b) and the compound (13) are both polymerizable, a usual polymerization inhibitor such as hydroquinone or catechol may be added to the reaction system if necessary. The amount of the base used is not particularly limited, but it is usually about stoichiometric amount. Compound (12)
The compounding ratio of the compound (13) and 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 mol of the compound (13).

The base used is not particularly limited and may be an ordinary one, for example, an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate, an organic base such as pyridine, piperidine, diisopropylamine, triethylamine or diazabicyclooctane. Can be mentioned.

Specific examples of the compound (13) include, for example, allyl halides or methallyl halides whose halogen atom is chlorine, bromine or iodine, 4-bromo-1-butene, 3-butenyl toluenesulfonic acid, benzenesulfonic acid. , An ester 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 the compound represented by the general formula [Chemical formula 14].

[0045]

HO-R ² Y [In the formula, R ² and Y are the same as defined above. ] (14)

This reaction is usually carried out in a solvent which does not affect the reaction, with heating if necessary. The compounding ratio of the compound (8) to the compound (14) is not particularly limited, but the compound (14) is usually 1.0 to
It may be used in a 3-fold molar amount, preferably in a 1.2- to 2-fold molar amount. Specific examples of the compound (14) include 2-
Halogeno-1-ethanol, 3-halogeno-1-propanol, 4-halogeno-1-butanol, 3-halogeno-2-methyl-1-propanol (wherein halogen atom is chlorine, bromine, iodine, etc.), benzenesulfonic acid -2-
Examples thereof include hydroxyethyl, 2-hydroxyethyl toluenesulfonate, 3-hydroxypropyl toluenesulfonate, and 4-hydroxybutyl toluenesulfonate.

Further, the compound (12) can also be produced, for example, as follows. That is, a compound represented by the general formula [Chemical Formula 15] in which the hydroxyl group of the compound (14) is protected by an appropriate functional group W is obtained, and this is reacted with the compound (8) to obtain the general formula [Chemical formula 1].
The compound (12) can be produced by obtaining the compound represented by [6] and further hydrolyzing the compound. W
Examples of the functional group represented by are acetyl group, tetrahydropyranyl group, methoxymethyl group, benzenesulfonyl group, toluenesulfonyl group and the like.

[0048]

Embedded image WO-R ² Y (14a)

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

[0050]

[Chemical 16]

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

The reaction of the compound (8) with the compound (14a) is carried out in a suitable solvent with heating, if necessary.
The solvent is not particularly limited as long as it does not affect the reaction, and for example, the same solvent as used in the synthesis of compound (8) can be used. The amount of the compound (14a) used is not particularly limited and can be appropriately selected from a wide range, but is usually about 1.0 to 3 times mol, preferably 1.2 to 2 times the mol of the compound (8).
It may be about double the mole. Specific examples of the compound (14a) include, for example, 2-halogenoethyl acetate, 2-halogenoethyl tetrahydropyranyl ether, 4-halogenobutyl toluenesulfonate (wherein the halogen atom is chlorine, bromine, iodine, etc.), ethylene glycol. Examples thereof include bisbenzene sulfonic acid ester and ethylene glycol bistoluene sulfonic acid ester.

The compound (12a) is hydrolyzed according to a conventional method. For example, the compound (12a) can be easily converted into the compound (12) by heating it in dilute hydrochloric acid as needed.

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

The polymer represented by the general formula [Chemical Formula 1] of the present invention is obtained by subjecting the compound (2) to a commonly used polymerization method such as solution polymerization, solid phase polymerization, bulk polymerization, emulsion polymerization or suspension polymerization. Although it can be produced, it is preferable to employ the solution polymerization method. The solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and for example, water, methanol, ethanol, a protic solvent such as propanol, ether, tetrahydrofuran, an ether solvent such as dioxane, Chloroform, halogenated hydrocarbons such as carbon tetrachloride, benzene, aromatic hydrocarbons such as toluene, acetonitrile, nitrile solvents such as propionitrile, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, dimethyl sulfoxide, etc. It may represent an aprotic polar solvent.

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

The solvent used when the solution polymerization method is adopted is not particularly limited as long as it does not adversely affect the reaction, and examples thereof 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,
An aprotic polar solvent such as dimethylacetamide, hexamethylphosphoric triamide, or dimethyl sulfoxide can be used. These solvents may be used as a mixture of two or more components.

The reaction temperature and reaction time will differ depending on the reactivity of the monomers and the type of solvent used, but are usually 0 to 100 ° C., 5
It is preferable to select in the range of 120 hours.

The homopolymer of the present invention is produced by polymerizing only the polymerizable monomer represented by the general formula (2) or two or more kinds of monomers.

The produced homopolymer can be isolated and purified by a usual post-treatment method. For example, by pouring the reaction mixture into an excess solvent in which the product is hardly soluble to cause precipitation, and separating by filtration or the like. It can be isolated. When further purification is necessary, a conventional method such as reprecipitation may be adopted.

The number average molecular weight Mn of the homopolymer of the present invention is
2,000 to 1,000,000, preferably 5,000 to 300,000, Mw /
Mn = 1.1 to 2.0 (Mw is a weight average molecular weight) is preferable. The degree of polymerization is determined by factors such as the concentration of raw materials in the polymerization reaction, the kind and concentration of the initiator, the reaction temperature, the reaction time, etc. Therefore, by selecting these factors according to the situation, the desired molecular weight and polydispersity can be obtained. A homopolymer can be obtained.

The obtained homopolymer is subjected to ion exchange according to a known method, and the counter anion is chloride ion, bromine ion, iodine ion, nitrate ion, perchlorate ion, acetate ion, methylsulfate ion or the like. It can be a divalent anion such as a valent anion, a sulfate ion, or a methylphosphate ion.

When the polymer of the present invention is used, one or two or more kinds of the above-mentioned active ingredient polymers can be mixed and used.

The polymer of the present invention can be in the form of powder, granules, fibers, films, 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, pool, fishing net, ship bottom, underwater structure, food packaging material, building material, agricultural material, medical product, oral material (toothbrush, toothpaste, etc.), eyeglass frame, cosmetics,
It is widely used in clothing and household items.

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

Specific examples of the object for which the antibacterial polymer can be used include synthetic polymers of all forms,
For example polypropylene, polyethylene, polystyrene,
Natural polymers such as polyester, polyamide, polyacrylate, polyurethane, polyvinyl chloride, etc., such as cotton, wool, feather, hemp, silk, paper, rubber, etc.
Further, wood, glass, metal, ceramic products and the like can be mentioned.

The shape of these objects may be a molded product or a raw material. For example, the antibacterial treatment can be carried out in a thread shape, a fiber shape, a film shape, a sheet shape, a granular shape, a powder shape, or the like.

The polymer of the present invention can impart antibacterial properties to these substances with high safety and excellent antibacterial activity for a long period of time.

When an antibacterial polymer is used, it is generally methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide. It is preferably dissolved in dimethylsulfoxide or the like, or dissolved in a mixed solvent of these solvents and acetone, tetrahydrofuran, benzene, toluene, xylene or the like for use. It is dissolved so that the concentration is 0.01 to 2.0% by weight, preferably 0.1 to 1.0% by weight. The substance to be imparted with antibacterial property is dipped in this solution, or the solution is applied to the surface by a method such as spraying the substance and then dried to remove the solvent. The drying temperature is 0 to 80 ° C, preferably
It is desirable to dry in a drying room at 20 to 60 ° C for 10 to 48 hours.

Further, the antibacterial polymer is also excellent in antifouling property in water. When the antibacterial polymer is used for antifouling in water, it can be mixed and used with a known film-forming composition, and at that time, a known antifouling component-containing substance can be added.

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

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, dimethyl sulfoxide. It is desirable to dissolve them in, or to use them in a mixed solvent system of these solvents and benzene, toluene, xylene and the like. As a usage method, a known method can be used.

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

Any known coating film-forming composition may be used as a mixture with the antibacterial polymer, and examples thereof include acrylic acid resin-based, phthalic acid resin-based and amino alkyd resin-based compositions. , Synthetic resin emulsion type and ratker.

[0076]

Embodiments will be described in detail below with reference to embodiments.

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 lauryl bromide was added thereto while stirring at room temperature. 10.0 g (0.04 mol) was added dropwise and subsequently heated at 70 ° C. for 3 hours. Then, the reaction solution was cooled to room temperature and the white precipitate formed was filtered to give N, N, N ', N'-tetramethyl-1,4.
-Diaminobutane-N, N'-dilauryl dibromide
0.12g was by-produced (by-product rate 1.0%). The filtrate was concentrated under reduced pressure, most of TMB was distilled off, the resulting white paste-like residue was washed with 40 ml of hexane, and the hexane layer was separated by decantation to obtain a white wax-like substance in which unreacted TMB was completely removed. Was obtained. When this was dried under reduced pressure with a vacuum pump, 14.5 g of N, N, N ', N'-tetramethyl-1,4-diaminobutane-N-lauryl bromide (hereinafter abbreviated as TML-C ₄ ) was produced. (Yield 92
%). ¹ H-NMR (CDCl ₃ ) δppm: 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 to 3.45 (m, 2H, CH ₂ N)

Examples 2 to 6 N, N, N ', N'-tetramethyl-1,3-diaminopropane (hereinafter abbreviated as TMP) 20.8 g instead of TMB
(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- 1,8-diaminooctane (hereinafter abbreviated as TMO) 32.0 g (0.16 mol), N,
36.5 g (0.16 mol) of N, N ', N'-tetramethyl-1,10-diaminodecane (hereinafter abbreviated as TMD) or N, N, N', N '
-Tetraethyl-1,6-diaminohexane (hereinafter TEH
The reaction and post-treatment were carried out in the same manner as in Example 1 except that 36.5 g (0.16 mol) was used to obtain the desired monoquaternary ammonium salt derivative. At this time, a small amount of bis-quaternary ammonium salt derivative was by-produced. The results are shown in Table 1. In the table, Et represents an ethyl group.

Examples 7 to 10 27.5 g (0.16 mol) of TMH was used instead of TMB, and hexyl bromide was used instead of lauryl bromide.
Reaction and post-treatment in the same manner as in Example 1 except that 6.6 g (0.04 mol), decyl bromide 8.8 g (0.04 mol), tetradecyl bromide 11.1 g (0.04 mol), or octadecyl bromide 13.3 g (0.04 mol) were used. Then, the desired monoquaternary ammonium salt derivative was obtained. At this time, a small amount of bis quaternary ammonium salt derivative was by-produced. The results are also shown in Table 1.

[0080]

[Table 1]

Example 11 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 thereto with stirring at room temperature. Then 5
When heated at 0 ° C for 17 hours, white crystals began to precipitate. The reaction solution was cooled to room temperature, the resulting white crystals were isolated by filtration, washed with cold acetone and dried to give N, N, N ', N'-tetramethyl-N-lauryl-N'-(4-vinyl) benzyl. Hexamethylenediammonium bromide chloride (T
Abbreviated as MLS-C ₆₎ was produced 12.0 g (yield: 87
%). ¹ H-NMR (CDCl ₃ ) δppm: 0.86 (t, 3H, CH
_{3), 1.92~1.37 (m, 18H} , CH 2), 1.53~1.73
(M, 6H, CH ₂ ), 1.98 to 2.21 (m, 4H, C
H ₂ ), 3.26 (s, 6H, CH ₃ N), 3.37 (s, 6H,
CH ₃ N), 3.40 to 3.50 (m, 2H, CH ₂ N), 3.68 to
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 12 to 15 Allyl bromide was used instead 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
Bis (quaternary) quaternary compound and N-2-tosyloxyethyl acrylamide (6.79 g, 24 mmol) and acetone or ethyl acetate as the solvent, and the reaction and post-treatment were conducted in the same manner as in Example 11. An ammonium salt derivative was obtained. The results are shown in Table 2.

[0083]

[Table 2]

Examples 16 to 24 In place of TML-C ₆ , TML-C ₃ 9.09 g (24 mmol), TML-C ₄ 9.43 g (24 mmol), TML respectively.
-C ₈ 11.7 g (26 _{mmol), TML-C 10 12.4g (} 26
_{Mmol), TMH-C 6 8.76g (} 26 mmol), TM
D-C ₆ 10.2g (26 _{mmol), TMT-C 6 11.7g (} 26 _{mmol), TMO-C 6 13.1g (} 26 mmol) or TE
Example 1 except that 12.4 g (26 mmol) of LC ₆ was used.
The reaction and post-treatment were carried out in substantially the same manner as in 1 to obtain the desired bis-quaternary ammonium salt derivative. The results are shown in Table 3.

[0085]

[Table 3]

Example 25 8.42 g (20 mmol) of TML-C ₆ obtained in Example 3 was dissolved in 200 ml of methanol, and 3-bromo-1 was added thereto at room temperature.
2.78 g (20 mmol) of propanol were added. Next, the mixture was heated to 50 ° C., 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 to remove the solution layer 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 (9.96 g, yield 89%). ¹ H-NMR (CDCl ₃ ) δppm: 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 to 3.59 (m, 8H, CH ₂ N)

Example 26 Except that 4.88 g (20 mmol) of 4-tosyloxy-1-butanol was used in place of 3-bromo-1-propanol, the reaction and post-treatment were carried out in substantially the same manner as in Example 25 to obtain N, N,
10.2 g of N ′, N′-tetramethyl-N- (4-hydroxy) butyl-N′-laurylhexamethylene diammonium bromide toluenesulfonate (TMLB-C ₆ ) was obtained as white crystals (yield 91%). ¹ H-NMR (CDCl ₃ ) δppm: 0.87 (t, 3H, C
_{H 3), 1.20~1.56 (m,} 28H, 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 to 3.63 (m, 10H, CH ₂ ), 3.75 (s, 1
H, OH), 7.55 (d, 2H, ArH), 7.86 (d, 2)
H, ArH)

Example 27 16.8 g (40 mmol) of TML-C ₆ obtained in Example 3 was dissolved in 200 ml of acetone, and 6.67 g (40 mmol) of 2-bromoethyl acetate was added thereto at room temperature. Mix the mixture at 50 ° C for 12
When the white crystals formed by the reaction for a time were isolated by filtration, N,
23.1 g of N, N ', N'-tetramethyl-N- (2-acetoxy) ethyl-N'-laurylhexamethylene diammonium dibromide was obtained. This was dissolved in 120 ml of 2% dilute hydrobromic acid, stirred at 60 ° C. for 15 hours, and the mixture was concentrated under reduced pressure. The obtained pale yellow wax was put into ethyl acetate for washing, and then the solution layer was filtered to remove 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 ) δppm: 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 28 5.46 g (10 mmol) of TMLE-C ₆ obtained in Example 27
And allyl bromide 1.45 g (12 mmol) dichloromethane 5
Dissolve in 0 ml and stir at room temperature with stirring 1.01 g (1
0 mmol) was added dropwise. The mixture was stirred at 40 ° C. for 15 hours, cooled to room temperature and the white precipitate formed was removed by filtration. The filtrate was concentrated to give a pale yellow wax. After thoroughly washing this with acetone and drying it,
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 ) δppm: 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 to 3.60 (m,
8H, CH ₂ N), 5.39 (d, 1H, vinyl), 5.68
(M, 1H, vinyl), 5.92 (d, 1H, vinyl)

Example 29 6.88 g (12 mmol) of TMLS-C _{6 was} added to 10 ml of methanol.
A solution obtained by dissolving 99 mg (0.6 mmol) of AIBN in 2 ml of methanol was added thereto. The mixture became a viscous solution when stirred at 65 ° C. for 22 hours under nitrogen atmosphere. The reaction solution was poured into water to stop the polymerization reaction, and the resulting white polymer was filtered and isolated, and dried under reduced pressure to obtain a white polymer. 6.80 g of a homopolymer of the raw material compound was obtained as a white powder by repeating the procedure of re-dissolving in methanol and introducing it into water several times for purification and drying (yield 99
%). The white powder was confirmed to be the target by TLC, IR and ¹ H-NMR analysis. When this product was subjected to GPC analysis (based on polystyrene) using dimethylformamide as a solvent, Mn = 204,000 and polydispersity Mw / Mn = 1.3. The total halogen content according to the oxygen flask combustion method (Analytical Chemistry Handbook) and the content of the quaternary ammonium group determined by the colloid titration method using polyvinyl potassium sulfate (PVSK) were 102% of the theoretical values.

Examples 30 to 37 6.47 g (10 mmol) of TMLK-C ₆ and TML respectively
C-C ₆ 7.04 g (10 mmol), TMLV-C ₄ 5.49 g
(10 mmol), TMLV-C ₁₀ 6.21 g (10 mmol), TMHV-C ₆ 4.89 g (10 mmol), TMTV
-C ₆ 6.01 g (10 _{mmol), TMOV-C 6 6.55g (} 10
Mmol) or TELV-C ₆ 6.28g (10 mmol) was dissolved in methanol 8ml this AIBN 82 mg (0.5 mmol) was added a solution obtained by dissolving in methanol 2 ml. Other reaction and post-treatment conditions and structural analysis were carried out in substantially the same manner as in Example 29 to obtain the intended homopolymer. The results are shown in Tables 4 and 5.

Example 38 5.42 g (10 mmol) of TMLA-C ₆ was dissolved in 8 ml of water, and 2,2'-bis (N-phenylamidinyl) -2,2'-was added thereto.
A solution of 50 mg of azopropane dihydrochloride in 2 ml of water was added. The mixture became a white gel when heated at 50 ° C. for 6 hours under nitrogen atmosphere. The reaction solution was poured into excess dioxane to stop the polymerization reaction. The resulting white precipitate was isolated by filtration and dried under reduced pressure to obtain 0.92 g of a homopolymer of the raw material compound as a white powder (yield 17%). This was confirmed to be the target compound by TLC, IR and ¹ H-NMR analysis. Gn analysis (polystyrene standard) using 20% water-containing methanol as a solvent, Mn = 60,000,
The polydispersity index was 1.8. The content of the quaternary ammonium group quantified in the same manner as in Example 29 was 99% of the theoretical value.

[0093] Examples 39 and 40 TMLA-C ₆ respectively TMLB-C ₆ 5.55g (10 mmol) or TML2A-C ₆ except that instead of 5.88 g (10 mmol) is substantially the same reaction as in Example 38, after The desired homopolymer was obtained by processing and structural analysis. The results are shown in Table 5.
It was shown to.

[0094]

[Table 4]

[0095]

[Table 5]

Comparative Example 1 77.0 g (0.74 mol) of styrene and 4-chloromethyl were used in a reaction for obtaining a copolymer from styrene (abbreviated as ST) and 4-chloromethylstyrene (abbreviated as CS) by a conventional solution polymerization. Styrene 9.2g (0.06mol) in tetrahydrofuran
60 in the presence of 0.66 g (4 mmol) of AIBN in 40 ml
The reaction was carried out at 0 ° C for 20 hours. The mixture was put into THF / methanol, purified by reprecipitation, isolated by filtration and vacuum dried to obtain 73.3 g of a white powdery polymer (abbreviated as PCS). The polymer was confirmed to be a two-component raw material copolymer by TLC, ¹ H-NMR, GPC analysis and the like.

From the results of the total halogen quantitative analysis and elemental analysis by the oxygen flask combustion method, the composition of ST and CS in PCS was 91.7: 8.3 in molar ratio. As a result of GPC measurement (converted to polystyrene) using THF as a solvent, the number average molecular weight of the PCS was Mn = 134,000 and the polydispersity was Mw / Mn = 1.57.

Next, 19.6 g of PCS obtained here was added to THF 500
7.0 ml of TML-C ₄ obtained in Example 1
(8 mmol) was added and reacted at 80 ° C. for 21 hours. The reaction mixture was cooled to room temperature, poured into water, and the precipitate was filtered and dried to obtain a white polymer. This was dissolved in methanol, reprecipitated twice in water for purification, and dried to obtain 23.4 g of a white powdery polymer. This is 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.

The total halogen content of the polymer was determined by the oxygen flask combustion method, the N% content by the elemental analysis method and the quaternary ammonium group content by the colloidal titration method were carried out to determine the content of ST unit, residual chloromethyl group, that is, unreacted C.
The S unit content and the TML-C ₄ unit loading amount were calculated, and these compositions were 91.7 mol% and 0.5, respectively.
% And 7.8 mol%.

Comparative Test Example 1 The polymers obtained in Example 29 and Comparative Example 1 were placed in a glass container. These were allowed to stand in a constant temperature bath whose temperature was controlled at 50 ° C under light-shielding conditions, and the changes over time were observed. After 1 week, no particular change was observed in the polymer of Example 29, whereas the product obtained in Comparative Example 1 produced an acidic gas which turned a little yellow and turned the pH test paper red. Similarly, after 20 days, the product obtained in Example 29 did not change in appearance and had good solubility in methanol, whereas most of the products obtained in Comparative Example 1 contained methanol and dimethylformamide (DM).
F) and the like were insoluble in components.

Test Example 1 Preparation of antibacterial processed cloth The compounds synthesized in Examples 29 to 40 were used as test compounds,
Each compound was dissolved in methanol to give 0.1, 0.2 and
A 0.5 wt% methanol solution was used. Next, cotton kanakin, J
An IS standard cloth (hereinafter abbreviated as cloth) was dipped in the methanol solution to impregnate the solution (padding method). Then, the weight was quickly measured, and after curing at 105 ° C. for 30 minutes, the test compound was sufficiently fixed to the cloth and used as a so-called “antibacterial processed cloth” in the following test.

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

From the above formula (1), the relationship between the W value and the C value is as follows. W: (Methanol of the test compound) C: (Concentration of the solution fixed on the antibacterial processed cloth) Weight of the test compound (wt%) (mg / g cloth) 0.1 1.0 0.2 0.2 0.5 5.0

Antibacterial Property Test The “antibacterial processed cloth” obtained as described above was used as a “test method for inhibiting bacterial growth of antibacterial processed fiber products” (hereinafter referred to as “antibacterial fiber test method”) of the Society for Antibacterial and Antifungal Society of Japan. (Abbreviated) was tested. The test bacteria are Pseudomonas aeruginosa.
Add ATCC 10145 to 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 edited by Japan Society of Antibacterial and Antifungal, Antibacterial and Antifungal Handbook, 1986, p678-69.
I referred to 1.

Display of results The display of the test results was as follows. Initial number of bacteria is N
(I), the number of bacteria after culture in the drug-added (sample) group is N (D)
As a result, the bactericidal index was calculated from the following equation (2). Bactericidal index = log N (I) -log N (D) (2)

Next, the sterilization index is divided into the following four stages, and when the sterilization index is less than 1 ... 1, when the sterilization index is 1 or more and less than 2 ... 2, the sterilization index is 2 or more and less than 3 The results are shown in Tables 6, 7 and 8 when the sterilization index is 3 and the sterilization index is 3 or more.

Comparative Example 2 After using a silicon type quaternary ammonium salt compound as a test compound and dissolving it in water, an antibacterial treated cloth was prepared according to the method of Test Example 1 and an antibacterial property test was conducted. The test compound concentration in the antibacterial processed cloth was the same as in Test Example 1. The results are shown in Tables 6, 7, and 8.

Comparative Example 3 A polymer type antibacterial compound having a group having an amphoteric surfactant function in its side chain was used as a test compound and dissolved in water, and then an antibacterial processed cloth was prepared according to the method of Test Example 1. Then, an antibacterial test was conducted. The test compound concentration in the antibacterial processed cloth was the same as in Test Example 1. The results are shown in Tables 6, 7, and 8.

Comparative Example 4 A silver-containing zeolite compound was used as a test compound, which was kneaded into nylon and spun to prepare a so-called kneaded nylon cloth, which was used as an antibacterial processed cloth in the method of Test Example 1. An antibacterial test was conducted in accordance with the above. The test compound concentration in the antibacterial processed cloth was the same as in Test Example 1. The results are shown in Tables 6 and 7,
8 shows.

[0110]

[Table 6]

[0111]

[Table 7]

[0112]

[Table 8]

Test Example 2 Effect of Laundry Treatment on Antibacterial Activity Among the antibacterial processed cloths obtained in Test Example 1, the test compound adhered has a concentration of 2.0 (mg / g cloth) JIS-L
The effect of the laundry treatment on the antibacterial activity was examined by conducting an antibacterial test according to Test Example 1 before and after the laundry treatment by the method of 0217 (1976), 103.

In each washing treatment, "Nitsusan Nonion NS-210" (manufactured by NOF CORPORATION) was used as a detergent at a rate of 0.5 g per 1 liter of water, and the water temperature was 40 ° C and the bath ratio was 1 : 5 by household electric washing machine at 30
It was washed for 5 minutes, and then washed for 5 minutes while overflowing with water. The results of the antibacterial test are shown in Tables 9 and 10.

[0115]

[Table 9]

[0116]

[Table 10]

[0117]

INDUSTRIAL APPLICABILITY 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08F 126/02 MNQ 7242-4J (72) Inventor Koji Mori 463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Kagaku Co., Ltd. Tokushima Research Institute (72) Inventor Mitsuo Akada 463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Tokushima Research Institute

Claims (2)

[Claims] 1. A homopolymer having a repeating unit represented by the general formula [Chemical Formula 1]. [Chemical 1] [In the formula, 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. The alkyl group of the number 6 to 18 is the same or different for R ^{5 to} R ^{8 and} has 1 to 3 carbon atoms.
Represents an alkyl group, and each may contain a substituent. A is a methylene _{group, -CH 2 O -, - CH} 2 CH 2 O
-, - CO -, - 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 each represents a monovalent anion, or both represent a divalent anion. ] 2. A method for producing a homopolymer, which comprises polymerizing a monomer represented by the general formula [Chemical Formula 2]. [Chemical 2] [In the formula, 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. The alkyl group of the number 6 to 18 is the same or different for R ^{5 to} R ^{8 and} has 1 to 3 carbon atoms.
Represents an alkyl group, and each may contain a substituent. A is a methylene _{group, -CH 2 O -, - CH} 2 CH 2 O
-, - CO -, - 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 each represents a monovalent anion, or both represent a divalent anion. ]