JPH09143186A - Quaternary ammonium group-containing disiloxane compound and antimicrobial algaecide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new quaternary ammonium group-containing disiloxane compound excellent in antimicrobial and algaecidal effect, low in foaming properties, high in thermostability, useful as an antimicrobial algaecide for skin, hair, clothing, tableware, medical too, etc. SOLUTION: This new quaternary ammonium group-containing disiloxane compound is shown by formula I (R<1> is a 8-20C hydrocarbon; R<2> to R<8> are each a lower alkyl; X<-> is a counter anion in the quaternary ammonium group; (m) is an integer of 1-6), is excellent in antimicrobial and algaecidal power and is useful for sterilizing, disinfecting and cleaning skin, hair, clothing, tableware, medical tool, floor or process of a food plant, useful as an antimicrobial algaecide for water treatment such as swimming pool, cooling water, etc., and as a disinfecting deodorant for train, hotel, gathering place, barn, etc. The compound is obtained by reacting a tertiary amine of formula II with a disiloxane compound of formula III (Y is a halogen).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a disiloxane compound having a novel quaternary ammonium salt, and a bactericidal / algicidal agent containing the compound as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, quaternary ammonium salts have been used as a cationic surfactant for various purposes, and it is known that some of them have a strong bactericidal / algicidal action. Among them, alkyldimethylbenzylammonium chloride (benzalkonium chloride) has been used in a wide range of fields due to its excellent bactericidal activity (the carbon chain length of an alkyl group is mainly C _{12 to} C ₁₄ ). On the other hand, as the organosilicon-based quaternary ammonium salt, 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride is known to exhibit an antibacterial action, and is used for the antibacterial and deodorant finishing of fibers. In addition, a method of suppressing the growth of algae by this compound is also known. (For example, JP-A-47-43345 and JP-A-48-5814.
5) However, this compound does not show a bactericidal effect that can be used in an aqueous system. In addition, Japanese Patent Laid-Open No. 2-6489
JP-A-3-43483 discloses that an organosilicon quaternary ammonium salt exhibits an antibacterial action.

[0003]

The above-mentioned quaternary ammonium salt has foamability in its aqueous solution system, is inferior in thermal stability, or is remarkably adsorbable to various material components,
In addition, the use of the active ingredient is limited due to the fact that the sterilization / algicidal action is reduced due to the release of the active ingredient to the outside and the separation and sedimentation inside.

[0004]

Means for Solving the Problems The present inventors have found a quaternary ammonium salt which has a sufficiently high bactericidal activity when used as a bactericidal and algicidal agent, is thermally stable without foaming and is useful in a wide range. As a result of diligent studies aimed at providing, a disiloxane compound having a specific quaternary ammonium group has extremely excellent bactericidal activity, algalicidal activity, and microbiocidal activity against bacteria, filamentous fungi, algae, and a wide range of other microorganisms causing trouble. The present invention has been completed by finding out that it has a low foaming property.

That is, the present invention provides the following general formula (I)

[0006]

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(Wherein R ¹ is a straight-chain hydrocarbon group having ^{8 to} 20 carbon atoms, R ^{2 to} R ⁸ are independently lower alkyl groups having 1 to 6 carbon atoms, and X ⁻ is a quaternary ammonium group. The present invention relates to a disiloxane compound having a quaternary ammonium group represented by a counter anion and m is an integer of 1 to 6, and a bactericidal / algicidal agent containing the compound as an active ingredient.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (I), the straight-chain hydrocarbon group represented by R ¹ and having 8 to 20 carbon atoms includes an octyl group, a nonyl group, a decyl group, a dodecyl group and tridecyl group. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, saturated hydrocarbon groups such as icosanyl group, octenyl group, octynyl group, decenyl group, decynyl group, dodecenyl group, dodecynyl group,
An unsaturated hydrocarbon group such as a tetradecenyl group, a tetradecynyl group, a hexadecenyl group, a hexadecynyl group, an octadienyl group, a dodecadienyl group, a pentadecatrienyl group and an octadecatrienyl group can be exemplified. The lower alkyl group having 1 to 6 carbon atoms represented by R ^{2 to} R ⁸ is a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a tert-butyl group, Examples thereof include a pentyl group and a hexyl group, but R
^{Of 4 to} R ⁸ , a methyl group is most preferable in terms of easiness of synthesis and price of raw materials.

In the above general formula (I), the counter anion in the quaternary ammonium group represented by X ⁻ is F ⁻ ,
Cl ⁻ , Br ⁻ , I ^−, etc., halogen ion, hydroxide ion,
Examples include conjugate bases of mineral acids such as carbonate ion, sulfate ion, hydrogen sulfate ion, sulfite ion, nitrate ion, and phosphate ion, and conjugate bases of organic acid such as carboxylate ion, sulfonate ion, and phosphonate ion. You can

The compound represented by the general formula (I) is
For example, it can be manufactured by the following method.
That is, the following general formula (II)

[0011]

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(Wherein R ¹ is a straight-chain hydrocarbon group having 8 to 20 carbon atoms, and R ² and R ³ are independently lower alkyl groups having 1 to 6 carbon atoms). An amine compound and the following general formula (III)

[0013]

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(Wherein R ^{4 to} R ⁸ are independently a lower alkyl group having 1 to 6 carbon atoms, Y is a halogen atom, and m is 1 to 6).
Is an integer. By reacting with a disiloxane compound having a haloalkyl group represented by the formula (1), a disiloxane compound having a repeating unit represented by the general formula (I) wherein X ⁻ is a halogen ion can be produced. When X ⁻ is other than a halogen ion, it can be easily obtained by ion-exchanging the halogen ion, which is the counter anion of the compound thus obtained, with the corresponding conjugate base such as a mineral acid or an organic acid.

This reaction may be carried out in a solventless system by mixing the above-mentioned two kinds of raw materials, but it is also possible to carry out in a solvent, and as a solvent to be used, each raw material is dissolved in the reaction. Any substance that does not participate may be used, and for example, methanol, ethanol, propanol, isopropanol, ethylene glycol, acetone, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethylsulfoxide and a mixed solvent thereof are preferably used. In addition, this reaction normally proceeds smoothly in the temperature range from room temperature to around 150 ° C.

The bactericidal / algicidal agent of the present invention contains the disiloxane compound of the present invention represented by the general formula (I) as an active ingredient, and various forms are conceivable. For example, the compound may be dissolved or dispersed in water or an aqueous solution of an inorganic salt to be used as a liquid agent, or may be supported on an appropriate carrier. Further, the compound may be dispersed in a polymer film or used as it is as a solid agent. Further, a liquid agent containing the compound may be applied to or impregnated into a molded body of fiber, glass, plastic or the like to impart a bactericidal / algicidal action thereto. Alternatively, the compound can be mixed with a detergent such as soap or shampoo. And, if necessary, as a mixture with alkyldimethylbenzylammonium chloride (benzalkonium chloride), which is a conventionally used quaternary ammonium salt agent, didecyldimethylammonium chloride, or polyhexamethylenebiguanidine hydrochloride, Alternatively, propionamides (for example, 2,2-dibromo-3-nitrilopropionamide) which are general industrial fungicides, nitroalcohol derivatives (for example, 2-bromo-2-nitropropane-1,3-diol, 2, 2-
Dibromo-2-nitroethanol etc.), isothiazolines (eg 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3)
-One, etc.), alkylenebisthiocyanates (eg, methylene-bisthiocyanate, ethylenebisthiocyanate, etc.), halogenated acetic acid ester derivatives (1,4
-Bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene, etc.) or a mixture of these agents even when they are mixed and used alternately at the site of use. It can be used without impairing the properties of the cationic fungicidal algicidal agent.

The bactericidal / algicidal agent containing the disiloxane compound of the present invention as an active ingredient is a sterilizer / disinfectant for skin, hair, clothes, tableware, medical instruments, etc., or an environment such as a floor of a food factory.
It can be used for disinfection or sterilization / washing of processes, and is also useful as a germicidal algaecide for water treatment of pools, cooling water, etc., or as a disinfecting deodorant for public facilities such as trains, hotels, and gathering places, livestock houses, etc. Is.

[0018]

EXAMPLES The present invention will be described in more detail below with reference to reference examples, examples and test examples. However, it goes without saying that the present invention is not limited to these.

Reference Examples 1 and 2

[0020]

[Chemical 6]

2.00 ml (9.05 mmol) of commercially available chloromethylpentamethyldisiloxane (manufactured by Chisso Corporation) and 6.79 g (45.3 mmol) of sodium iodide were dissolved in 10 ml of 2-butanone and refluxed under an argon atmosphere. , Reacted overnight. After the solvent was distilled off, the residue was extracted with diethyl ether, washed with water, and the organic phase was dried over anhydrous sodium sulfate. When the solvent was completely distilled off again under reduced pressure, 1.86 g of iodomethylpentamethyldisiloxane represented by the above formula (1) was obtained as a pale brown liquid. (Yield; 71%) ¹ H-NMR of compound (1)
The spectrum is shown below.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.08 (9H, s),
0.13 (6H, s), 2.52 (2H, s).

Further, in the above reaction, 7.50 g of 3-chloropropylpentamethyldisiloxane was used in place of chloromethylpentamethyldisiloxane, and 20.0 g of sodium iodide and 30 ml of 2-butanone were used, respectively, and the same operation as above was carried out. This was carried out to obtain 8.21 g of 3-iodopropylpentamethyldisiloxane represented by the above structural formula (2) as a pale brown liquid. (Yield; 78%) ¹ H-NMR of compound (2)
The spectrum is shown below.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.08 (9H, s),
0.13 (6H, s), 0.63 (4H, m), 1.33 (4H, m), 3.20 (2
H, t, J = 6.0Hz).

Examples 1, 2

[0026]

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0.70 g of the compound (1) obtained in Reference Example 1 (2.
42 mmol) and N, N-dimethyloctylamine 0.50 ml (2.42 mmo
l) were mixed and reacted at 100 ° C. for 24 hours. Then 10^-1tor
Distill away unreacted materials by heating at 100 ° C for 2 hours under vacuum of r or less.
As a result, the quaternary ammonia represented by the above structural formula (3)
0.93 g of a disiloxane compound having an um group was added to a brown viscous solid.
Obtained as body. (Yield; 78%) The product has the above-mentioned structure.
Being made is the following ¹1 H-NMR, IR and Mas
It was confirmed from the s spectrum.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.13 (9H, s),
0.35 (6H, s), 0.86 (3H, s), 1.21-1.35 (12H, m),
3.26 (2H, s), 3.43 (6H, s), 3.62 (2H, m). IR (KBr, cm ^-1 ); 2900, 1730, 1610, 1460, 1260 (Si-
C), 1050 (SiOSi), 840.Mass (m / z); 318 (M ⁺ -I), 204,
156, 147, 133, 73, 58.

Further, in the above reaction, N, N-dimethyldodecylamine was used in place of N, N-dimethyloctylamine.
The same operation as described above was performed using 05 ml of the compound (1) and 1.10 g to obtain 1.61 g of a disiloxane compound having a quaternary ammonium group represented by the above structural formula (4) as a brown viscous solid. (Yield: 84%) ¹ H—N of compound (4)
The MR, IR and Mass spectra are shown below.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.13 (9H, s),
0.36 (6H, s), 0.87 (3H, s), 1.25 (14H, m), 1.36 (4
H, m), 1.63 (2H, m), 3.27 (2H, s), 3.44 (6H, s),
3.62 (2H, m). IR (KBr, cm ^-1 ); 2900, 2850, 1720, 1460, 1410, 137
0, 1260 (Si-C), 1150 (SiOSi), 840. Mass (m / z); 374 (M ⁺ -I), 204, 147, 73, 58.

Examples 3, 4

[0032]

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2.00 g (6.) of the compound (2) obtained in Reference Example 2
32 mmol) and N, N-dimethyloctylamine 0.99 g (6.32 mmol)
Was dissolved in 20 ml of methanol and reacted under reflux for 24 hours.
After distilling off the solvent, the solution is vacuumed at 10 ^-1 torr or less at 100 ° C for 2
After heating for an hour to distill off the unreacted material, 2.50 g of a disiloxane compound having a quaternary ammonium group represented by the above structural formula (5) was obtained as a brown viscous solid. (Yield: 8
3%) Note, that the product has the structure of the above-mentioned below of the ¹ H
-Confirmed from NMR, IR and Mass spectra.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.07 (9H, s),
0.10 (6H, s), 0.55 (1H, t, J = 8.3Hz), 0.63 (1H, t,
J = 8.3Hz), 0.87 (3H, t, J = 6.6Hz), 1.26 (6H, m), 1.
37 (4H, m), 1.70 (2H, m), 1.82 (2H, m), 3.32 (3H,
s), 3.38 (3H, s), 3.50 (4H, m). IR (KBr, cm ^-1 ); 2950, 2870, 1470, 1420, 1260 (Si-
C), 1160 (SiOSi), 850.Mass (m / z); 346 (M ⁺ -I), 232,
147, 73, 58.

Further, in the above reaction, N, N-dimethyldodecylamine was used in place of N, N-dimethyloctylamine 2.
Using 02 g, 3.00 g of the compound (2) and 20 ml of methanol, respectively, the same operation as above is carried out to obtain 4.32 g of the disiloxane compound having a quaternary ammonium group represented by the above structural formula (6) in a brown viscosity. Obtained as an individual. (Yield: 8
6%) ¹ H-NMR, IR and Mass of compound (6)
The spectrum is shown below.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.06 (9H, s),
0.09 (6H, s), 0.54 (1H, t, J = 8.4Hz), 0.62 (1H, t,
J = 8.4Hz), 0.86 (3H, t, J = 6.6Hz), 1.24 (14H, m),
1.35 (4H, m), 1.71 (2H, m), 1.81 (2H, m), 3.31 (3
H, s), 3.38 (3H, s), 3.50 (4H, m). IR (KBr, cm ^-1 ); 2950, 2860, 1470, 1420, 1280 (Si-
C), 1100 (SiOSi), 880.Mass (m / z); 402 (M ⁺ -I), 232,
212, 147, 73, 58.

Test Example 1 (Confirmation of bactericidal activity against bacteria and filamentous fungi) The disiloxane compounds obtained in Examples 1 to 4 were tested for bactericidal activity. The types of strains used in the test, their methods and results are shown below.

(1) Test strains Six strains of bacteria and two strains of filamentous fungi, which are industrially important obstacles, were selected and a total of eight strains shown below were tested. Bacteria Bs: Bacillus subtilis IFO3007 (Bacillus subtilis) Ec: Escherichia coli NIHJ (E. coli) Pa: Pseudomonas aeruginosa IAM1054 (Pseudomonas aeruginosa) Sa: Staphylococcus aureus ATCC6538p (Staphylococcus aureus) Ss: Shigella sonnei (Shigella tyrum) St: Salmonium (S. typhimurium) Filamentous fungus An: Aspergillus niger ATCC6275 (black mold) Ps: Penicillium steckii IAM7048 (blue mold)

(2) Test method The disiloxane compounds obtained in Examples 1 to 4 were accurately weighed and diluted with water to prepare 100 μg / ml preparations. Using this preparation, 100, 50, 25,
Each of them was diluted to a concentration of 10, 5, 2.5 and 1 μg / ml to prepare a sample solution. Next, the test strains stored in the test tube were put into a test tube into which 10 ml of ordinary broth medium (three grams of meat extract, 10 g of peptone and 5 g of sodium chloride dissolved in 1,000 ml of water) was dispensed with a platinum loop and placed at 30 ° C. 48
After culturing for a period of time, the solution stored at 20 ° C. was used as the culture solution of the test bacteria. 9 ml of the above sample solution was placed in a sterilized 10 ml L-shaped test tube, and 1 ml of the culture solution of the test bacteria was inoculated into the sterilized test tube and allowed to act with the drug at 30 ° C. for 30 minutes. After the action, this liquid 1
After adding 1 ml to 100 ml of sterilized water and uniformly diluting it, 1 ml of this diluted solution was taken as a working solution. The strains in these working solutions were further cultured by the methods described below, and the bactericidal activity of each compound was determined. Bacteria: 10 μl of the working solution was placed in a sterilized petri dish, 5 ml of a culture medium for bacteria (tryptosoya agar medium manufactured by Nissui Pharmaceutical Co., Ltd.) was poured and solidified, and the mixture was cultured at 30 ° C. for 2 days. Filamentous bacterium: 5 ml of a medium for filamentous fungus (potato dextrose agar medium manufactured by Nissui Pharmaceutical Co., Ltd.) was poured into a sterile petri dish to solidify, 10 μl of the working solution was added, and the mixture was cultured at 30 ° C. for 4 days.

For the determination of the bactericidal activity, colonies of each bacterium and filamentous fungus were visually observed, and those in which the medium was clear and no colonies could be determined were killed. The lowest concentration of the sample solution from which the bacteria were killed was defined as the minimum bactericidal concentration of the compound.

(3) Test Results Table 1 shows the minimum bactericidal concentrations of each bacterium and filamentous fungus when each of the compounds obtained in Examples 1 to 4 was used. As can be seen from Table 1, all of these disiloxane compounds were found to exhibit excellent bactericidal activity at extremely low concentrations. In addition, for comparison, benzalkonium chloride (compound (7)) and 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride (compound (8)) were prepared from the disiloxane compounds obtained in Examples 1 to 4. Instead, the results of conducting the same sterilizing power test as above are shown in Table 1.

[0042]

[Table 1] Table 1 ─────────────────────────────────── Minimum bactericidal concentration (μg / ml) No. Bs Ec Pa Sa An Ps Ss St ─────────────────────────────────────────────────────────────────────────────────────────────────────────────────── 3) 2.5 5 5 2.5 10 2.5 2.5 1 (4) 5 2.5 5 2.5 10 5 2.5 2.5 (5) 2.5 1 5 1 5 2.5 1 1 (6) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Comparative compound number (7) 10 25 5 10 25 10 25 10 (8)> 100> 100> 100> 100> 100> 100> 100> 100 ──────────────────────── ──────────── (Note) Compound number (7) is benzalkonium chloride Compound number (8) is 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride

Test Example 2 (Confirmation of Algicidal Activity against Algae) The disiloxane compounds obtained in Examples 1 to 4 were tested for algicidal activity. The types of algae used in the test, their methods and results are shown below.

(1) Test algae-Green alga Chlorella vulgaris-Cyanobacteria Oscillatoria chlorina (2) Test method The above-mentioned green algae and cyanobacteria were collected in a Detmer medium at 25 ° C.
Cultivate in the artificial weather machine of to make the test solution. Then Detmer
1/3 dilution of the medium [Ca (NO ₃ ) ₂ 1.0 g KCl 0.25 g MgSO 4
_{4 · 7H 2 O 0.25g KH 2} PO 4 0.25g FeCl 3 0.002g / H 2 O
3l] and add the chemical solution and the test solution to the specified concentration.
Incubate in a climate machine at ℃. The culture is continuously stirred with a stirrer. After 48 hours, the decolorized state of the algae is observed, and the lowest effective concentration is defined as the minimum algicidal concentration. (3) Test results Table 2 shows the minimum algicidal concentration of each drug. As can be seen from Table 2, it was found that all the disiloxane compounds obtained in Examples 1 to 4 exhibited excellent algicidal activity at an extremely low concentration. In addition, for comparison, benzalkonium chloride (compound (7)) and 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride (compound (8)) were prepared from the disiloxane compounds obtained in Examples 1 to 4. Instead, the results of the same algicidal test as above are shown in Table 2.

[0045]

[Table 2] Table 2 ────────────────────────────────── Minimum algicidal concentration (μg / ml) No. Chlorella vulgaris Oscillatoria chiorina ─────────────────────────────────── Example compound number (3) 5 2.5 ( 4) 2.5 2.5 (5) 5 1 (6) 2.5 2.5 Comparative compound numbers (7) 5 5 (8) 25 10 ──────────────────────── ──────────── (Note) Drug number (7) is benzalkonium chloride Drug number (8) is 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride

Test Example 3 (Foamability Test) The disiloxane compounds obtained in Examples 1 to 4 were examined for foamability. The method and results are shown below.

(1) Test method 10 μg of the disiloxane compound obtained in Examples 1 to 4
/ Ml aqueous solution is prepared. 50 ml of this liquid is 100 m
Place in a graduated cylinder with a 1-liter stopper and shake vigorously up and down 5 times and let stand. After standing, read the thickness of the foam after 20 seconds on the scale of the graduated cylinder.

(2) Test results Table 3 shows the foaming properties of the compounds obtained in Examples 1 to 4. As can be seen from Table 3, these disiloxane compounds were found to have lower foamability than conventional quaternary ammonium salts. For comparison, benzalkonium chloride (compound (7)) was used in place of the disiloxane compounds obtained in Examples 1 to 4, and the same foamability test as above was conducted. Shown together.

[0049]

[Table 3] Table 3 ──────────────────────── Number Foam thickness ──────────────── ───────── Example compound numbers (3) <1 (4) <1 (5) <1 (6) 3 Comparative compound numbers (7) 9 ────────── ─────────────── (Note) Drug number (7) is benzalkonium chloride

[0050]

The compound of the present invention has excellent bactericidal / algicidal activity, low foaming property and high thermal stability, and is therefore useful as a wide range of bactericidal / algicidal agents.

The bactericidal / algicidal agent containing the disiloxane compound of the present invention as an active ingredient is a sterilizer / disinfectant for skin, hair, clothes, tableware, medical instruments, etc., or an environment such as a floor of a food factory.
It can be used for disinfection or sterilization / washing of processes, and is also useful as a germicidal algaecide for water treatment of pools, cooling water, etc., or as a disinfecting deodorant for public facilities such as trains, hotels, and gathering places, livestock houses, etc. Is.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Kazunori Tanaka, Shioshin, Hamada, Fukuda-cho, Iwata-gun, Shimooka 328 Kainoi Kasei Co., Ltd. Hamano 328 Kai Kasei Co., Ltd. (72) Inventor Masahiro Morita Shioshin, Fukuda-cho, Iwata-gun Shizuoka Hamano 328 Kai AI Kasei Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the following general formula (I) (In the formula, R ¹ is a linear hydrocarbon group having 8 to 20 carbon atoms,
R ^{2 to} R ⁸ are independently a lower alkyl group having 1 to 6 carbon atoms, X ⁻
Is a counter anion in the quaternary ammonium group, and m is an integer of 1 to 6. And a disiloxane compound having a quaternary ammonium group. 2. The following general formula (I): (In the formula, R ¹ is a linear hydrocarbon group having 8 to 20 carbon atoms,
R ^{2 to} R ⁸ are independently a lower alkyl group having 1 to 6 carbon atoms, X ⁻
Is a counter anion in the quaternary ammonium group, and m is an integer of 1 to 6. ) A bactericidal / algicidal agent containing a disiloxane compound having a quaternary ammonium group represented by the formula (1) as an active ingredient.