JPH0692811A - Antibacterial agent - Google Patents

Abstract

PURPOSE:To provide an antibacterial agent containing an organosilicone phosphonium salt as an active component, having broad antibacterial spectrum and exhibiting sufficient antibacterial effect by the contact for a short time. CONSTITUTION:This antibacterial agent contains, as an active component, the compound of formula I [R1 is alkoxy, halogen or acyl; one of R1 may be OH; R2 is (substituted) <=20C bivalent hydrocarbon group or <=20C bivalent hydrocarbon group containing O and N; R3 to R5 are H, OH, 1-20C straight or branched chain alkyl, aryl or aralkyl (the alkyl, etc., may be substituted with OH or alkoxy); X is anion], e.g. 3-(trimethoxysilyl)-propyl triethyl phosphonium chloride. The compound of formula I can be produced by reacting an organosilicone of formula II with a phosphine derivative of formula III. Various products such as paper, wood, rubber, plastic, fiber and paint can be imparted with antiseptic property and antibacterial property by applying the compound to the product by immersion, spraying, roller-coating, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antibacterial agent, and more particularly to an antibacterial agent containing an organosilicone phosphonium salt as an active ingredient.

[0002]

2. Description of the Related Art At present, a great variety of antibacterial agents are used in various fields such as industry, agriculture and food. Most of the antibacterial agents that have been used so far have been synthetic antibacterial agents with a high degree of toxicity, but recently, research aimed at reducing the toxicity of antibacterial agents has progressed and they are insoluble in water. Silicone-type and polymer-type immobilized antibacterial agents that exhibit almost no toxicity have been developed. These immobilized antibacterial agents can impart a bactericidal function to the surface of various substances, and are used in many fields including, for example, antibacterial and deodorant fibers fixed to the surface of fibers.

As a polymer-type immobilized antibacterial agent, it has been reported that a pendant type antibacterial agent is immobilized on a polymer such as polyvinyl, polyacrylate, polymethacrylate, polyester and polyamide. For example, an alkylpyridinium salt and an alkyldimethylbenzylammonium salt are fixed to a polyvinyl chain, biguanides are fixed to a polyacrylate chain and a polymethacrylate chain, and an alkylpyridinium salt is fixed to a polyester chain and a polyamide chain. Has been done.

The silicone-type immobilized antibacterial agent is obtained by immobilizing an alkoxysilyl group-introduced antibacterial agent through a dealcoholization reaction and a dehydration reaction with a hydroxyl group on the surface of a carrier, for example, 3- (trimethoxy). Quaternary ammonium salt forms such as silyl) propyldimethylalkylammonium chloride have been mainly developed. Among these immobilized antibacterial agents, most of the compounds that are in practical use or under research are quaternary ammonium salt-based compounds.

[0005]

However, although the quaternary ammonium salt-based immobilized antibacterial agent has a broad antibacterial spectrum, the antibacterial effect of acting on microorganisms by contact for a short time is not yet sufficient.

Therefore, an object of the present invention is to solve the above-mentioned problems and to provide an antibacterial agent having a broad antibacterial spectrum and having a sufficient antibacterial effect by contact for a short time.

[0007]

As a result of earnest research, the present inventors have found that certain organosilicone phosphonium salts exhibit extremely strong antibacterial activity, and completed the present invention.

That is, the antibacterial agent according to the present invention has the following general formula:

[Chemical 2] (In the formula, R ₁ is selected from the group consisting of an alkoxy group, a halogen atom and an acyl group, one may be a hydroxyl group, and R ₂ has ₂ carbon atoms which may have a substituent.
A divalent hydrocarbon group of 0 or less, or a divalent hydrocarbon group of 20 or less carbon atoms containing an oxygen atom or a nitrogen atom, wherein R ₃ , R ₄ and R ₅ are hydrogen atoms and a hydroxyl group. ,
A linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group is shown, and the alkyl group, aryl group and aralkyl group may be substituted with a hydroxyl group or an alkoxy group, and X is an anion. Represents an organosilicone phosphonium salt as an active ingredient.

In the organosilicon phosphonium salt of the above general formula (1) which is an active ingredient of the antibacterial agent of the present invention,
Specific examples of R _{1 in} the formula include alkoxy groups such as methoxy group, ethoxy group and propoxy group, halogen atoms such as chlorine and bromine, acetyl group, propionyl group, acyl groups such as acryloyl group, _One of R ₁ may be a hydroxyl group. R ₁ is preferably an alkoxy group such as a methoxy group or an ethoxy group.

Next, specific examples of R _{2 in} the above general formula (1) have substituents such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, ethylethylene group and the like. A divalent carbon-hydrogen group having 20 or less carbon atoms or a divalent hydrocarbon group having 20 or less carbon atoms containing an oxygen atom or a nitrogen atom, which is a methylene group, an ethylene group, A lower alkylene group such as a tetramethylene group is preferred.

Further, specific examples of R _{3 to} R _{5 in} the above general formula (1) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and dodecyl group. An alkyl group such as an octadecyl group, a phenyl group, a tolyl group, an aryl group such as a xylyl group, a benzyl group, an aralkyl group such as a phenyl group, a hydroxyl group, and an alkoxy group, and a heptyl group is preferable. , Octyl group, dodecyl group, alkyl group such as octadecyl group, phenyl group, aryl group such as tolyl group, and more preferably octyl group having 6 or more carbon atoms, dodecyl group, alkyl group such as octadecyl group,
It is a phenyl group. Note that R ₃ , R ₄ and R ₅ may be the same group or different groups.

X ⁻ is an anion, for example, a halogen ion such as fluorine, chlorine, bromine or iodine, a carboxyl ion such as formic acid, acetic acid and oxalic acid, a sulfate ion, a phosphate ion, methyl or dimethylphosphate ion, ethyl or Examples thereof include diethyl phosphate ion, antimony fluoride ion, phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion, perchlorate ion and the like, and among them, halogen ion is preferable.

In the organosilicone phosphonium salt according to the general formula (1), one of all three of R _{3 to} R ₅ is different from the same kind, and one of them is 6 kinds of carbon atoms regardless of the same kind or different kinds. More than one, especially alkyl groups having a size larger than the octyl group are preferable because the antibacterial activity tends to be higher.

Examples of such organosilicon phosphonium salts include 3- (trimethoxysilyl) -propyltriethylphosphonium chloride, 3- (trimethoxysilyl) -propyltributylphosphonium chloride, 3- (trimethoxysilyl) -propyltrioctylphosphonium. Chloride, 3- (trimethoxysilyl)-
Propyltriphenylphosphonium chloride, 3-
(Trimethoxysilyl) -propyldimethyloctadecylphosphonium chloride, 3- (trimethoxysilyl)-
Propyldiethyloctadecylphosphonium chloride, 3- (trimethoxysilyl) -propyltrioctylphosphonium bromide, 3- (trimethoxysilyl)-
Propyltridodecylphosphonium bromide, 3-
(Trimethoxysilyl) -propyltrioctylphosphonium iodide, 3- (trimethoxysilyl) -propyltridodecylphosphonium iodide, 3- (trimethoxysilyl) -propyltributylphosphonium tetrafluoroborate, 3- (trimethoxysilyl) -Propyltrioctylphosphonium perchlorate, 3- (trimethoxysilyl) -propyltrioctylhexafluorophosphate and the like.

The organosilicon phosphonium salt represented by the above general formula (1) may be produced by any method, and one example thereof is shown below as an industrial production method. An organosilicone represented by the general formula: (R ₁ ) ₃ —Si—R ₂ X (2) (wherein R ₁ and X have the same meanings as described above);

[Chemical 3] By reacting with a phosphine derivative represented by the formula (wherein R ₃ , R ₄ and R ₅ are as defined above), the organosilicone phosphonium salt represented by the above general formula (1) can be obtained.

The above reaction is preferably carried out in the presence or absence of an organic solvent at a reaction temperature of 50 to 200 ° C. for 1 hour or more. The organosilicone represented by the general formula (2) is preferably used in an equimolar to 1 to 2 times the molar amount of the phosphine derivative represented by the general formula (3). After completion of the reaction, the unreacted material is washed with a solvent such as n-hexane or ether to obtain the organosilicone phosphonium salt represented by the general formula (1).

The antibacterial agent of the present invention has an excellent antibacterial effect against Gram-positive bacteria, Gram-negative bacteria, molds, algae, yeasts, etc., that is, an antibacterial effect against bacteria, an antifungal effect against algae, and an antialgal effect. Have. Moreover, the organosilicon phosphonium salt is more stable to heat than the quaternary ammonium salt and other organic compounds, has a high decomposition temperature of around 250 ° C., and is chemically stable. There is a nature.

The organosilicon phosphonium salt according to the present invention can be used for various products such as paper, wood, rubber, plastics, fibers and paints by a commonly used method such as a dipping method, a spraying method, a roller coating method and a flow coating method. Etc. can be given antiseptic and antibacterial properties. Further, a carrier such as a desired solvent or powder, an auxiliary agent such as a surfactant, a coloring material, a dispersant, or other organic or inorganic antibacterial agent may be blended depending on the use and purpose.

[0019]

EXAMPLES Hereinafter, the antibacterial agent of the present invention will be further described with reference to examples. Example 1 After thoroughly replacing a 300 ml flask with nitrogen, 50.78 g (0.245 mol) of tributylphosphine was charged, the temperature was raised to about 125 ° C., and 52.16 of 3-chloropropylmethoxysilane was added.
g (0.249 mol) was added dropwise in about 80 minutes. After the dropping was completed, the reaction was performed at about 130 ° C. for 10 hours. The completion of the reaction was confirmed by a color reaction between tributylphosphine and carbon disulfide. After completion of the reaction, the reaction mixture was washed with n-hexane three times, and then concentrated at a maximum of 5 Torr at 70 ° C. for 2 hours to remove low boiling impurities such as a solvent. As a result, 94.9
3 g of oil was obtained. This one is 60MHz ¹ H-NM
When R, IR (KBr), and GC-MS (FAB) structural analyzes were performed, it was confirmed to be 3- (trimethoxysilyl) -propyltributylphosphonium chloride (Sample A).

Example 2 After thoroughly replacing a 300 ml flask with nitrogen, 58.93 g (0.193 mol) of trihexylphosphine was charged, the temperature was raised to about 150 ° C., and 42.92 of 3-chloropropylmethoxysilane was added.
g (0.205 mol) was added dropwise in about 80 minutes. After the dropping was completed, the reaction was carried out at about 155 ° C. for 10 hours. The completion of the reaction was confirmed by a color reaction between trihexylphosphine and carbon disulfide. After completion of the reaction, the reaction mixture was washed with n-hexane three times, and then concentrated at a maximum of 5 Torr at 70 ° C. for 2 hours to remove low boiling impurities such as a solvent. As a result, 9
Obtained 0.94 g of an oil. This one, 60MHz ¹ H
-NMR, IR (KBr), and GC-MS (FAB) structural analysis confirmed that it was 3- (trimethoxysilyl) -propyltrihexylphosphonium chloride (Sample B).

Example 3 After fully replacing a 300 ml flask, 71.41 g (0.179 mol) of trioctylphosphine was charged, the temperature was raised to about 185 ° C., and 39.33 of 3-chloropropylmethoxysilane was added.
g (0.188 mol) was added dropwise in about 80 minutes. After completion of dropping, the reaction was carried out at about 185 ° C. for 20 hours. The completion of the reaction was confirmed by a color reaction between trioctylphosphine and carbon disulfide. After completion of the reaction, the reaction mixture was washed with n-hexane three times and then at 70 ° C. for 2 times to remove low boiling impurities such as solvent.
Concentration was performed for a maximum of 5 torr. As a result, 92.
73 g of oil was obtained. This one, 60MHz ¹ H-
When NMR, IR (KBr), and GC-MS (FAB) structural analyzes were conducted, it was confirmed to be 3- (trimethoxysilyl) -propyltrioctylphosphonium chloride (Sample C).

<Antibacterial activity test> As a representative of Gram-positive bacteria, Staphylococcus aureus IFO12732 and as a representative of Gram-negative bacteria, Escherichia Coli IFO0
Samples of various organosilicone phosphonium salts obtained in the examples were applied to 3806 at the concentrations and the action times shown in Tables 1 and 2. The obtained antibacterial activity results are shown in Tables 1 and 2. The antibacterial activity was evaluated by a solution dilution method in which a predetermined amount of bacteria were ingested and brought into contact with each other, and then the number of bacteria was measured. It is indicated that the bactericidal activity is stronger as the number of bacteria is significantly reduced with respect to the contact time. As the samples B and C, samples dissolved in methanol were used. Also.
The container used for the test was a Teflon container.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

The antibacterial agent containing the organosilicone phosphonium salt of the present invention as an active ingredient has a broad antibacterial spectrum and exhibits a sufficient antibacterial effect by contact for a short time.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiko Kanazawa 9-15-1, Kameido, Koto-ku, Tokyo Nihon Kagaku Kogyo Co., Ltd. Research & Development Division (72) Inventor Fumihiko Okuyama 9-15, Kameido, Koto-ku, Tokyo No. 1 Inside R & D Headquarters of Nippon Kagaku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. The following general formula: (In the formula, R ₁ is selected from the group consisting of an alkoxy group, a halogen atom and an acyl group, one may be a hydroxyl group, and R ₂ has ₂ carbon atoms which may have a substituent.
A divalent hydrocarbon group of 0 or less, or a divalent hydrocarbon group of 20 or less carbon atoms containing an oxygen atom or a nitrogen atom, wherein R ₃ , R ₄ and R ₅ are hydrogen atoms and a hydroxyl group. ,
A linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group is shown, and the alkyl group, aryl group and aralkyl group may be substituted with a hydroxyl group or an alkoxy group, and X is an anion. Represents an organosilicon phosphonium salt as an active ingredient.