JP3205063B2 - Polymerizable monomer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable monomer and a method for producing the same. According to the present invention, a polymerizable monomer which is excellent in bactericidal activity, has high safety and stability, and can easily lead to an antibacterial polymer which can maintain its efficacy over a long period of time. Provided.

The antibacterial polymer derived from the polymerizable monomer of the present invention can be used, for example, for disinfection of tap water, cooling water, pool water, etc., slime control, antifouling of fishing nets, ship bottoms, underwater structures and the like. It can be used in a wide range of applications such as compositions, food packaging materials, building materials, agricultural materials, medical products, oral materials (toothbrushes, toothpastes, etc.), eyeglass frames, cosmetics, clothing, household goods, and the like.

[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 comprising a repeating unit represented by the general formula [Chemical Formula 6] (JP-A-61-100254) and those comprising a repeating unit represented by the general formula [Chemical Formula 7]. (JP-A-61-246205) and the like are known.

[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 [Chemical Formula 8] 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 ] to obtain a quaternary ammonium salt monomer represented by the general formula [Chemical Formula 9], which is copolymerized with acrylonitrile to obtain a polymer [(Research on Fiber Polymer Materials). Research Report No. 159 (1988), pp. 17-2
2]. However, these polymers also do not have sufficiently satisfactory antimicrobial activity.

[0015]

Embedded image

Further, in US Pat. No. 4,092,201, for example, a cationic monomer represented by the formula [Formula 10] is obtained.
This is polymerized to produce a polymer, but it is only described that the polymer is used as an adsorbent or is effective in improving antistatic and dye acceptance, etc. No mention is made of its use in applications. 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]

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[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antibacterial polymer which has excellent bactericidal activity, high safety and stability, and can maintain its efficacy for a long period of time. To provide a polymerizable monomer that can be used.

[0019]

According to the present invention, there is provided a compound represented by the general formula:
And a method for producing the same.

[0020]

Embedded image

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; ⁴ represents an alkyl group having 6 to 18 carbon ^atoms, R 5 to R ⁸ is shows the same or different connexion alkyl group having 1 to 3 carbon atoms. 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 represent a monovalent anion, or both represent a divalent anion. ]

In the compound of the present invention represented by the general formula (1), the alkylene group represented by R ³ has 4 or 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 general formula (1), the anions represented by X and Y are not particularly limited as long as they can neutralize the positive charge. For example, chloride ions, bromine ions, iodine ions, nitrate ions Monovalent anions such as perchlorate, acetate, methylsulfate, benzenesulfonate, chlorobenzenesulfonate, and toluenesulfonate; and divalent anions such as sulfate and methylphosphate. Can be mentioned.

[0024] In the above general formula (1), the group represented by A is a methylene group, - CO -, - CO- N (R 9) -,
(R ⁹ is the same as described above) or the compound (1a) of the present invention, which is a vinylene group, is obtained by, for example, reacting a compound represented by the general formula [Formula 2] with a compound represented by the general formula [Formula 3]. Can be manufactured.

[0025]

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[0026] [in the ^{formula, R} 3 ~ R ⁸ 及 beauty X are the same as above. A ¹ is a methylene group, - CO -, - CO- N
(R ⁹ ) —, (R ⁹ is as defined above) or a vinylene group. ]

[0027]

Embedded image

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 (1a) and the compound (3) 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 (2) and the compound (3) is not particularly limited and can be appropriately selected from a wide range, but the compound (3) is usually about 0.7 to 1.2 moles, preferably 0.9 to 1.0 times the mole of the compound (2).
What is necessary is just to use about twice mol.

The mono-quaternary ammonium salt derivative represented by the general formula (2) is, for example, a lower alkyl group-substituted alkane diamine derivative represented by the general formula [Chemical Formula 11].
It is produced by reacting the compound represented by 2] without solvent or in a solvent, if necessary, with heating.

[0031]

Embedded image

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

[0033]

Embedded image R ⁴ X [R ⁴ is the same as above] (12)

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 (11) and the compound (12) 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 (11) with respect to the compound (12).
It may be about 2.5 times mol.

Specific examples of compound (11) 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 compound (12) 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 (3) 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 -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.

Furthermore in the general formula (1), the group represented by A is -CH ₂ O -, - Table with CH ₂ CH ₂ O-in which the present invention compound (1b), for example the general formula [Formula 4] And a compound represented by the general formula [Chemical Formula 5].

[0038]

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

[0040]

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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, if necessary, with heating. The solvent is not particularly limited as long as it does not affect the reaction, and examples thereof include ether, tetrahydrofuran, dichloromethane, chloroform, dimethylformamide, and dimethylsulfoxide. At the time of the reaction, since both the target compound (1b) and the compound (5) are polymerizable, ordinary polymerization inhibitors such as hydroquinone and 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 (4) to the compound (5) is not particularly limited, but the compound (4) may be used usually in an amount of about 0.7 to 1.2 times, preferably about 0.9 to 1.0 times, the compound (5). .

The base can be any conventional one 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 compound (5) include, for example, allyl halide or methallyl halide in which the halogen atom is chlorine, bromine or iodine, 4-bromo-1-butene,
Examples thereof include 3-butenyl toluenesulfonic acid, benzenesulfonic acid, esters of toluenesulfonic acid or chlorobenzenesulfonic acid with allyl alcohol or methallyl alcohol, and 2,3-dichloropropene.

Compound (4) is a known substance.
It can be produced by reacting compound (2) with a compound represented by the general formula [Formula 13].

[0046]

Embedded image HO—R ² Y wherein R ² and Y are the same as above. ] (13)

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 (2) and the compound (13) is not particularly limited, but the compound (13) is usually added to the compound (2) in an amount of from 1.0 to 1.0.
It may be used in an amount of about 3 moles, preferably about 1.2 to 2 moles. Specific examples of the compound (13) 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 (4) can be produced, for example, as follows. That is, a compound represented by the general formula [Chemical Formula 14] in which the hydroxyl group of the compound (13) is protected by an appropriate functional group W is obtained, and this is reacted with the compound (2) to obtain a compound of the general formula [Chemical Formula 1]
Compound [4] can be produced by obtaining the compound represented by 5] and further hydrolyzing the compound. Examples of the functional group represented by W include an acetyl group, a tetrahydropyranyl group, a methoxymethyl group, a benzenesulfonyl group, and a toluenesulfonyl group.

[0049]

Embedded image WO-R ² Y (13a)

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

[0051]

Embedded image

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

The reaction between compound (2) and compound (13a) 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 (2) can be used. The amount of the compound (13a) to be used is not particularly limited and can be appropriately selected from a wide range, but is usually about 1.0 to 3 times, preferably 1.2 to 2 times, the mole of the compound (2).
What is necessary is just to make it about 2 times mol. Specific examples of the compound (13a) include 2-halogenoethyl acetate, 2-halogenoethyl tetrahydropyranyl ether, 4-halogenobutyl toluenesulfonate (where the halogen atom is 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 (4a) is carried out according to a usual method. For example, by heating the compound (4a) in diluted hydrochloric acid as needed, the compound (4) can be easily prepared.
Can be converted to

The compounds of the present invention and their intermediates obtained by the above-mentioned reactions can be isolated and purified by usual means such as filtration, extraction, concentration and recrystallization.

[0056]

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 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 6 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- 1,8-diaminooctane (hereinafter abbreviated as TMO) 32.0 g (0.16 mol), N,
N, N ', N'-tetramethyl-1,10-diaminodecane (hereinafter abbreviated as TMD) 36.5 g (0.16 mol) or N, N, N', N '
-Tetraethyl-1,6-diaminohexane (hereinafter referred to as 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 a bisquaternary ammonium salt derivative was by-produced. Table 1 shows the results. In the table, Et represents an ethyl group.

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

[0060]

[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 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 12 to 15 Allyl bromide was substituted for 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-tosyloxyethylacrylamide, and reacted and worked up in the same manner as in Example 11 except that acetone or ethyl acetate was used as a solvent. An ammonium salt derivative was obtained. Table 2 shows the results.

[0063]

[Table 2]

[0064] Each TML-C ₃ 9.09g (24 mmol) in place of Example _{16~24 TML-C 6, TML-} C 4 9.43g (24 mmol), TML
-C ₈ 11.7 g (26 mmol), TML-C ₁₀ 12.4 g (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 Example 1 to obtain the desired bis quaternary ammonium salt derivative. Table 3 shows the results.

[0065]

[Table 3]

[0066] Example 25 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)

[0067] was added thereto 2-bromoethyl acetate 6.67 g (40 mmol) 16.8 g TML-C ₆ obtained in Example 26 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 27 5.46 g (10 mmol) of TMLE-C ₆ obtained in Example 26
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)
4.2 g of ethyl-N'-lauryl hexamethylene diammonium dibromide was obtained as almost white crystals (yield 72
%). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.86 (t, 3
_{H, CH 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 28 TMLP-C ₆ obtained in Example 25 in place of TMLE-C ₆
The reaction and after-treatment were carried out in the same manner as in Example 27 except that 5.60 g (10 mmol) was used to obtain the desired N, N, N ', N'-
Tetramethyl-N- (2-allyloxy) propyl-
3.9 g of N'-lauryl hexamethylene diammonium dibromide was obtained as almost white crystals (65% yield). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.88 (t, 3H, C
_{H 3), 1.21~1.60 (m,} 26H, CH 2), 1.63~1.80
_{(M, 4H, CH 2)} , 3.12 (d, 2H, CH 2 O), 3.
24 (t, 2H, CH ₂ O), 3.40 (s, 6H, CH
_{3 N), 3.54 (s,} 6H, CH 3 N), 3.45~3.61 (m,
8H, CH ₂ N), 5.41 (d, 1H, vinyl), 5.66
(M, 1H, vinyl), 5.90 (d, 1H, vinyl)

Comparative Example 1 (Polymer of US Pat. No. 4,092,201) N, N, N ', N'-tetramethyl-N- obtained in Example 25
5.60 g (10 mmol) of (3-hydroxy) propyl-N'-lauryl hexamethylene diammonium dibromide, 50 mg of hydroquinone and methacrylic acid chloride
1.15 g (11 mmol) was dissolved in 40 ml of dichloromethane and stirred at room temperature. 0.87 g (11 mmol) of pyridine
After slowly adding dropwise, stirring was continued for 18 hours as it was, and the resulting white precipitate was removed by filtration. The filtrate was concentrated to give a pale yellow wax, which was thoroughly washed with acetone and dried to give N, N, N ', N'-tetramethyl-N
4.89 g of -methacryloxypropyl-N'-laurylhexamethylenediammonium dibromide was obtained as almost white crystals (yield 78%). ¹ H-NMR (CDCl ₃ ) δ ppm: 0.87 (t, 3H, C
_{H 3), 1.20~1.57 (m,} 26H, CH 2), 1.63~1.81
_{(M, 4H, CH 2)} , 2.03 (s, 3H, CH 3), 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), 5.72 (s, 1H, vinyl), 6.27 (s, 1
H, vinyl)

3.14 g of N, N, N ′, N′-tetramethyl-N-methacryloxypropyl-N′-laurylhexanemethylenediammonium dibromide obtained above
(5 mmol) and 5.21 g (50 mmol) of styrene were dissolved in 10 ml of methanol, and a solution of 40 mg (0.25 mmol) of AIBN dissolved in 1 ml of methanol was added. The mixture was reacted at 65 ° C. for 22 hours under a nitrogen atmosphere to give a slightly cloudy viscous solution. The reaction solution was poured into a large amount of 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 this in methanol and throwing it into water was repeated twice to purify and dry to obtain 5.7 g of a white powdery polymer.
From the results of TLC, IR and ¹ H-NMR analysis, the white powder was confirmed to be a copolymer of diammonium dibromide and styrene as raw materials.

GPC analysis (based on polystyrene) using dimethylformamide as a solvent gave Mn = 6.1.
The polydispersity Mw / Mn was 1.7. By determining the content of quaternary ammonium groups by a colloid titration method using polyvinyl potassium sulfate (PVSK), the copolymer composition of starting material diammonium dibromide and styrene was 8:92.

Reference Example 1 (Synthesis of polymer) 3.44 g (6 mmol) of TMLS-C ₆ obtained in Example 11
And 5.62 g (54 mmol) of styrene were dissolved in 10 ml of methanol, and a solution of 50 mg (0.3 mmol) of AIBN dissolved in 2 ml of methanol was added thereto. Mixture under nitrogen atmosphere
Stirring at 65 ° C. for 22 hours resulted in a viscous solution. The reaction solution was post-treated in the same manner as in Comparative Example 1 to obtain 6.3 g of a white powdery polymer. The white polymer is TLC, IR and ¹ H-N
It was confirmed that the results of the MR analysis, a copolymer of TMLS-C ₆ and styrene.

When GPC analysis was performed in the same manner as in Comparative Example 1, Mn =
158,000 The polydispersity was Mw / Mn = 1.4. Copolymer composition of TMLS-C ₆ and styrene by quantifying the amount of O connexion quaternary ammonium group in the colloid titration 1
3:87.

Test Example 1 Preparation of Antibacterial Finished Cloth The compounds synthesized in Reference Example 1 and Comparative Example 1 were used as test compounds.
And a 0.5 wt% methanol solution. 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, after quickly measuring the weight, the sample was cured at 105 ° C. for 30 minutes, and the test compound was sufficiently fixed on the cloth.
It was used for the following tests as "antibacterial processed cloth".

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%)

From the above equation (1), 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 fabric” obtained as described above was used in combination with the “Bacterial Growth Inhibition Test Method for Antibacterial Processed Textile Products” of the Japan Society of Bacteria and Fungi 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 Results The test results were displayed as follows. N for the number of initial bacteria
(I) N (D)
The bactericidal index was determined from the following equation (2). Disinfection index = log N (I) -log N (D) (2)

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 Tables 4, 5, and 6.

Reference Example 2 3- (trimethoxylyl) -propyldimethyloctadecyl ammonium chloride was used as a test compound and dissolved in water. Then, an antibacterial processed cloth was prepared according to the method of Test Example 1, and an antibacterial test was conducted. Went. The test compound concentration in the antibacterial cloth was the same as in Test Example 1. The results are shown in Tables 4, 5, and 6.

Reference Example 3 Dodecyl-di (aminoethyl) glycine was used as a test compound and dissolved in water. Then, an antibacterial cloth was prepared according to the method of Test Example 1, and an antibacterial test was conducted. The test compound concentration in the antibacterial cloth was the same as in Test Example 1. Table 4 shows the results.
5 and 6.

Reference Example 4 250 g of fine powder of synthetic zeolite was sampled, and 500 ml of a 0.1 M silver nitrate aqueous solution was added. The resulting mixture was stirred at room temperature for 5 hours to carry out ion exchange. After filtering the silver-zeolite obtained by the ion exchange method, it was washed with water to remove excess silver ions. Next, the washed silver-zeolite was dried at 100 to 105 ° C. and then pulverized to obtain a fine silver-zeolite powder.

Next, the relative viscosity was measured with 95% sulfuric acid.
The resulting mixture was added to a 6-nylon dry chip of 2.3 so as to have a concentration of 0.1, 0.2 and 0.5% by weight, and then mixed.

Next, this nylon was melt-spun according to a conventional method, and then drawn to obtain a drawn yarn of 120 denier / 4 filament. Next, the drawn yarn was knitted into a cloth, then refined, and this was used as an antibacterial processed cloth and subjected to an antibacterial test according to the method of Test Example 1. The results are shown in Tables 4, 5, and 6.

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[Table 4]

[0087]

[Table 5]

[0088]

[Table 6]

Test Example 2 Influence of Laundry Treatment on Antibacterial Activity Among the antibacterial processed cloths obtained in Test Example 1, those having a fixed test compound concentration of 2.0 (mg / g cloth) JIS-L
The antibacterial test was carried out according to Test Example 1 before and after the washing treatment according to the methods of No. 0217 (1976) and 103 to examine the effect of the washing treatment on the antibacterial activity.

In each washing process, "Nitsusan Nonion NS-210" (manufactured by Nippon Oil & Fats Co., Ltd.) was used as a detergent at a rate of 0.5 g per liter of water, at a water temperature of 40 ° C. and a bath ratio of 1 g. ： 5 by home electric washing machine at 30
After washing for 5 minutes, the product was washed with water while overflowing with water for 5 minutes. Tables 7 and 8 show the results of the antibacterial test.

[0091]

[Table 7]

[0092]

[Table 8]

[0093]

Industrial Applicability According to the present invention, a polymerizable compound having excellent sterilizing power, high safety and stability, and which can easily lead to an antibacterial polymer which can maintain its efficacy over a long period of time. A monomer is obtained.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 225/06 C07C 225/06 231/22 231/22 233/38 233/38 (72) Inventor Yuji Hama Kawauchi, Tokushima City, Tokushima Prefecture 463 Kagasuno-cho, Otsuka Chemical Co., Ltd. Tokushima Research Laboratories (72) Inventor Mitsuo Akada 463 Kagasuno, Kawauchi-cho, Tokushima-shi, Tokushima Pref. Otsuka Chemical Co., Ltd. Tokushima Research Laboratories (56) References JP-A-5-139942 (JP, A) JP-A-5-139943 (JP, A) JP-A-5-139944 (JP, A) JP-A-5-201842 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C07C 211/63 C07C 209/12 C07C 209/20 C07C 221/00 C07C 225/06 C07C 231/22 C07C 233/38 C07C 209/60 CA (STN) )

Claims (3)

(57) [Claims] 1. A polymerizable monomer represented by the general formula [1]. 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.
Shows the to 3 alkyl group. A is a methylene 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
Represents the same or different monovalent anions or both represent divalent anions. ] 2. The method for producing a polymerizable monomer according to claim 1, wherein the compound represented by the general formula [Chemical Formula 2] is reacted with the compound represented by the general formula [Chemical Formula 3]. Embedded image [Wherein, R ³ represents 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 represent an alkyl group having 1 to 3 carbon atoms which are the same or different. You . X represents a monovalent anion. ] [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, and A ¹ represents a methylene group, —CO—, —CO—N ( R ⁹ )
—, (R ⁹ represents a hydrogen atom or a methyl group) or a vinylene group. m represents 0 or 1. Y represents a monovalent anion. ] 3. The polymerizable monomer according to claim 1, wherein the compound represented by the general formula [Chem. 4] and the compound represented by the general formula [Chem. 5] are reacted in the presence of a base. Production method. Embedded image [Wherein, 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 is an alkyl group having 6 to 18 carbon atoms, and R ^{5 to} R ⁸ are the same. Or a different number of carbon atoms
Shows the to 3 alkyl group. X and Y are the same or different and represent a monovalent anion, or both represent a divalent anion. ] [In the formula, R ¹ represents a hydrogen atom, a methyl group, a chloro group or a cyano group. A ² represents a methylene group or an ethylene group.
Z is a halogen atom, a lower alkoxy group having 1 to 4 carbon atoms,
It represents a lower acyloxy group having 2 to 5 carbon atoms, a benzenesulfonyloxy group, a chlorobenzenesulfonyloxy group, a tosyloxy group or a methanesulfonyloxy group. ]