JPH07285809A - Antibacterial agent containing quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To obtain an antibacterial agent highly potent in germicidal/sterilizing activity, also presenting its efficacy in a short time, and long in efficacy sustaining time. CONSTITUTION:This antibacterial agent contains several kinds of compound of formula I [R1 is a 6-18C alkyl or benzyl; R2 is H, a 1-18C alkyl, a 8-18C alkenyl or an aralkyl; R3 is a 12-22C alkyl; R4 is a 8-18C alkyl or of formula II (R5 is a 2-22C alkyl; (n) is 2 or 3); Y is an anion composed of one or three halogen atom(s)] and satisfies one or both of the following conditions: (A) the number of the molecules of the compound (where, R3 is a 16C alkyl) accounts for >=80% of the total number of the molecules of the compound; and (B) the anions composed of three halogen atoms accounts for >=50% of the total anions. This antibacterial agent is additionally incorporated with at least one kind among phosphoric esters of formula III (x and y total 3; R6 is a 3-20C organic group; (p) is 1 or 2), polyethanolamines of formula IV (z is 2-10; R7 is a 2-22C alkyl) and ammonium oxides of formula V (R8 is a 4-18C alkyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sterilizing / sterilizing agent containing quaternary ammonium and halogen. More specifically, it relates to a novel, low-toxicity, quaternary ammonium fungicidal composition, which is a mixture of polyethylene amide, ammonium oxide, and orthophosphoric acid polyester. Preferred anions as halogen are chlorine, iodine, and trihalogen. Compared with conventional sterilizers, this sterilizer has a very strong sterilizing and sterilizing effect and exerts an effect in a short time, suppressing the growth of viruses, bacteria, bacterial spores, fungi, etc.,
It also kills, so its use is widespread.

[0002]

2. Description of the Related Art Many bactericides for killing microorganisms and preventing their growth have been proposed so far. Some bactericides and disinfectants generate free halogens, which utilize the strong chemical affinity of free halogens to change by directly binding to organic substances, or to sterilize by utilizing strong oxidizing action. It is a thing.

As one example thereof, a quaternary ammonium compound (hereinafter referred to as QUAT) can be mentioned. This is a compound of nitrogen, which is a compound in which four groups are bonded to nitrogen by C—N bonds. Quaternary ammonium compound (QU
In AT), the nitrogen atom has a positive charge, and an anion is required to neutralize this positive charge. This compound can be easily prepared by combining a quaternary amine and a halogen, for example, US Pat. No. 4,66.
No. 8,273, International Patent Publication PCT, WO91 /
15120, and there is a large body of literature on the efficacy of these fungicides.

Particularly, an n-alkyltrimethylammonium salt (n-Alkyltr) represented by the following general formula
imemmyl ammonium salts, alkylbenzyl dimethyl ammonium salt (Alkyl)
benzeldimethyl ammonium s
Alts) is a well-known compound.

[Chemical 6]

Here, R'is a linear or side chain alkyl group or alkylene group, n is an integer of 1 to 20, and A is an anion such as halogen, acetic acid, sulfuric acid or phosphoric acid. The degree of bactericidal action of this bactericide on microorganisms varies depending on the length of the alkyl group or the like, that is, the number of carbon atoms, and the form, that is, whether it has a straight chain type or a side chain. Appl.M
icrobiology 14, No.3 (1966) p. 308, Lett. Appl. Microb
According to iology 1 (1985) p. 101, it is concluded that these fungicides exert their maximum effect when the linear alkyl group has 14 to 16 carbon atoms.

This quaternary ammonium compound (QUAT)
Despite their high bactericidal performance and low toxicity, these bactericides are rarely used in practice. This is because there are few types of bacteria that have a bactericidal effect, such as dimethylbenzyl ammonium chloride (dimethyl benzyl).
alkyl quaternary ammoniu
m chloride, or benzalconium
Chloride) is a well known fungicide.

Halogens such as chlorine, iodine, fluorine,
Bromine has a bactericidal action and has been widely used as a disinfectant. However, they do have some drawbacks. Iodine is often used as a disinfectant as iodine tincture, but when used at a high concentration in order to enhance the bactericidal effect, it has a serious irritation to human tissues and is harmful. Further, there is a problem of decolorization and coloring. Chlorine and bromine are also often used as disinfectants and germicides, but they have problems of corrosion and irritation.

Although many halogen-containing bactericides have been developed so far, complete bactericides have not yet been developed. They can be divided into two types, known as iodophors, which release free halogens in use and those which are always chemically bound to halogens.
The sterilizing power of the former can utilize the sterilizing power of halogen, but the latter cannot utilize all the sterilizing power of halogen. Also, US Pat. No. 4,824,867 and US Pat.
No. 883,917, number 4 from halogen and ammonium
It is described to produce an ammonium compound (QUAT).

The disadvantages of the conventional water-soluble halogen-containing germicides are that halogen is rapidly ionized and that the vapor pressure at room temperature is low, so that the duration of germicidal effect is short. The halogen of the quaternary ammonium compound (QUAT) does not contribute to the increase of bactericidal activity. However, when the anion is trihalogen alone or a mixture thereof, the liberation and release of halogen becomes slow, so that the bactericidal power is increased.

[0010]

DISCLOSURE OF THE INVENTION The fungicide of the present invention is
It eliminates the disadvantages of the conventional fungicides mentioned above, and when used alone or in combination with other fungicides, it covers a wide range of pH against almost all viruses, bacteria, bacterial spores and fungi. Even at a low concentration, it exhibits a bactericidal effect against bacteria and the like in a short time.
Further, the present invention provides a disinfectant having high stability and a long effective period, and having no disinfectant odor.

[0011]

In order to solve the above problems, the present invention provides the following general formula (I):

[Chemical 7] [In the formula, R ₁ is an alkyl group having 6 to 18 carbon atoms or a benzyl group; R ₂ is a hydrogen atom, 1 to 1 carbon atoms.
An alkyl group having 8 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, or an aralkyl group; R ₃ has 12 to 12 carbon atoms;
22 alkyl groups; R ₄ has 8 to 18 carbon atoms
Alkyl groups or the following formula (II):

[0012]

[Chemical 8] (Wherein R ₅ is an alkyl group having 2 to 22 carbon atoms, and n is 2 or 3); and Y is an anion composed of 1 or 3 halogen atoms. In the antibacterial agent comprising a plurality of molecules defined by the following conditions: (a) the ratio of the number of molecules having an alkyl group having 16 carbon atoms as R ₃ is all molecules within the above definition. 80 for number
% Or more; (b) of the monovalent anions defined as Y, the ratio of anions consisting of three halogen atoms is 50% or more with respect to the number of anions within the definition of Y above; There is provided an antibacterial agent characterized by satisfying (a) or (b), or both (a) and (b).

The present invention also provides a method of using the above germicides. In the present invention, in addition to the above conditions, the following conditions are further added: (c) The ratio of the number of molecules having a benzyl group as R ₁ is
70% or more with respect to the number of molecules within the above definition; (d) The ratio of the number of molecules having an alkyl group with 14 to 16 carbon atoms as R ₂ is 40% with respect to the number of molecules within the above definition. Of the above, among them, an antibacterial agent satisfying (c) or (d) or both (c) and (d) is preferable.

In the present invention, an antibacterial agent satisfying both (a) and (b) is preferable, and an antibacterial agent satisfying all the conditions (a) to (d) is more preferable. In a preferred embodiment of the present invention, in the definition relating to the above formula (I), the following conditions are satisfied: (a ′) The ratio of the number of molecules having an alkyl group having 16 carbon atoms as R ₃ is all molecules within the above definition. 9 for number
0% or more; (b ') The proportion of anions consisting of three halogen atoms among the monovalent anions defined as Y is 70% with respect to the anions within the definition of Y; Of these, a bactericide satisfying (a ') or (b') or both (a ') and (b') is preferable.

In the definition of (I) above, the above conditions: (a ') or (b') or both (a ') and (b') are satisfied, and the following condition: (c ') R The ratio of the number of molecules having a benzyl group as ₁ is 80% or more with respect to the number of molecules within the above definition; (d ′) The ratio of the number of molecules having an alkyl group having 14 to 16 carbon atoms as R ₂ is 50% or more based on the number of molecules within the above definition; of (c ′) or (d ′),
Alternatively, an antibacterial agent satisfying both (c ') and (d') is particularly preferable. In the present invention, an antibacterial agent satisfying both of the above conditions (a ') and (b') is particularly preferable, and further, all of the above conditions (a '), (b'), (c ') and (d'). Antibacterial agents satisfying the above are particularly preferable.

[0016]

DETAILED DESCRIPTION The present invention provides an antibacterial agent comprising a plurality of molecular species having a structure defined by the above formula (I). There are a large number of molecular species defined by the formula (I), but in the present invention, at least one of the conditions (a) and (b) must be satisfied, and the conditions (a) and (b) must be satisfied. Those satisfying (4) are particularly preferable.

Satisfying the condition (a) means the following. Any of the numerous molecular species defined by formula (I)
_At position ₃ , it has one of the substituents defined for R ₃ . In an aggregate of such molecular species,
It means that the ratio of the number of molecules having an alkyl group having 16 carbon atoms as R ₃ , that is, a cetyl group, is 80% or more of the total number of molecules within the definition of the formula (I). Conditions (b), (c), (d), (a '), (b'),
(C ') has the same meaning. The upper limit of the numerical values of these conditions is 100%, which means that, for example, with respect to R ₃ , all molecules belonging to the definition of formula (I) are R
It means that it has a cetyl group as ₃ .

The synthesized product is a group of molecules having various substituents in any of the substituents. For example, a group of molecules in which R ₃ is a cetyl group (100%) is obtained by purifying the product. To be However, as a component of the antibacterial agent of the present invention, the antibacterial component does not need to be a single molecule, and highly refined is not a good idea from the viewpoint of cost. Therefore, the value is 100% under each condition.
Does not necessarily have to be

The ratio of the number of molecules having an alkyl group (cetyl group) having 16 carbon atoms as R ₃ is 80% or more (condition a) with respect to the total number of molecules within the definition of the above formula (I). Yes, preferably 85% or more, more preferably 9
It is 0% or more (condition a '), and most preferably 95% or more. Among the monovalent anions defined as Y, the ratio of anions composed of three halogen atoms is 50% or more (condition b) with respect to the number of anions within the definition of Y, and preferably 60. % Or more, more preferably 7
0% or more (condition b '), more preferably 80%
Or more, and most preferably 90% or more.

The ratio of the number of molecules having a benzyl group as R ₁ is 70% or more (condition c), preferably 80% or more (condition c '), more preferably the number of molecules having the above-mentioned definition. Is 90% or more. The ratio of the number of molecules having an alkyl group having 14 to 16 carbon atoms as R ₂ is 40% or more (condition d), preferably 50% or more, with respect to the number of molecules within the definition of the formula (I). (Condition d '), more preferably 60% or more, most preferably 70% or more.

As many of the above conditions as possible are satisfied, and as the ratio of the molecular species specified under the above conditions increases, the toxicity to humans and mammals decreases and the antibacterial spectrum becomes low. It tends to become wider, which is preferable. In the definition of each substituent, the alkyl group may be a straight chain alkyl group or a branched chain alkyl,
A straight chain alkyl group is preferable from the viewpoint of easy availability.

In the definition of Y, the c
Rogen is fluorine, chlorine, bromine, and iodine, and chlorine
And iodine are particularly preferred. Consists of one halogen molecule
Anion is Cl^-, Br^-Or I^-And preferably
Is Cl^-Or I^-And I ^-Is particularly preferable. The present invention
Anion consisting of three halogen atoms that constitutes the characteristics of
(Monovalent anion) consists of the same halogen atom
Of different halogen atoms may also be used.
Yes. 3 as an anion composed of the same halogen atom
Anion I consisting of individual iodine atoms₂I^-Is preferred,
Examples of anions composed of different halogen atoms include salts.
Consisting of iodine and iodine, especially I₂Cl ^-, ICl₂
^-, Or I₂I^-Is preferred.

The antibacterial composition of the present invention may contain only the quaternary ammonium salt represented by the formula (I) as an active ingredient, but preferably, in addition to the quaternary ammonium salt represented by the formula (I), the following additions are made. It is preferable to contain at least one of the above components. (1) The following formula (III):

[0024]

[Chemical 9] (In the formula, the sum of x and y is 3, and R ₆ has 3 carbon atoms.
To 20 organic groups and p is 8 to 14); (2) the following formula (IV):

[0025]

[Chemical 10] (In the formula, z is an integer of 2 to 10 and R ₇ is an alkyl group having 2 to 22 carbon atoms); (3) The following formula (V):

[0026]

[Chemical 11] (In the formula, R ₈ is an alkyl group having 4 to 18 carbon atoms). Formula (III)
The phosphoric acid ester represented by is a surfactant and functions as a catalyst that facilitates a chemical reaction during the synthesis of the component of formula (I) and the like. The polyethanolamine represented by the formula (IV) increases stability while eliciting higher stability. The ammonium oxide represented by the formula (V) forms bubbles for giving a smooth feeling to the skin of the human body.

Preferably, the total of one or more additional components is 30 to 10 parts by weight based on 70 to 90 parts by weight of the quaternary ammonium salt represented by the formula (I). Preferably, the quaternary ammonium salt represented by the formula (I) is 70-
When 90% by weight of the surface-active phosphate ester (1) of the formula (III) is used, the amount thereof is 3 to 7 parts by weight, and when the polyetal amine of the formula (IV) is used, The amount is 5 to 15 parts by weight, and when the ammonium oxide of the formula (V) is used, the amount is 5 to 10 parts by weight.

Particularly preferably, in addition to the quaternary ammonium salt of the formula (I), it contains all the additional components of the formulas (III) to (V). Particularly preferably, it comprises, in addition to the quaternary ammonium salt of the formula (I), all the additional components of the formulas (III) to (V), the amount of which is based on the total amount of the formula (I).
The quaternary ammonium salt of the formula (1) has an anion consisting of 3 halogen atoms and 68 to 72 parts by weight, and the quaternary ammonium salt of the formula (I) has an anion consisting of one halogen atom. 6-10 parts by weight, 3-7 parts by weight of the phosphoric acid ester of the formula (III), 8-12 parts by weight of the polyethanolamine of the formula (IV), and 5 parts by weight of the ammonium oxide of the formula (V). ~ 9 parts by weight.

A preferred embodiment comprises, in addition to the quaternary ammonium salt of formula (I), all the additional components of formulas (III) to (V), the approximate amount of which is 70 parts by weight of the quaternary ammonium salt of (I) having an anion composed of 3 halogen atoms, and 1 part of the quaternary ammonium salt of the formula (I) having an anion composed of 1 halogen atom. Is 8 parts by weight, formula (II
5 parts by weight of the phosphoric acid ester of I), 10 parts by weight of the polyethanolamine of the formula (IV) and 8 parts by weight of the ammonium oxide of the formula (V).

In the antibacterial composition of the present invention, the aforementioned antibacterial component, ie the quaternary ammonium salt of formula (I), as well as the additional components of formulas (III) to (V), are present in the composition medium. can do. In such an antibacterial composition, the above antibacterial component is preferably 0.0001% by weight.
Present in the range of up to 100% by weight. An aqueous medium or an organic solvent is used as the composition medium. As the aqueous medium, water or an aqueous buffer solution having a pH of 2 to 12, preferably a pH of 5 to 8.5, such as a phosphate buffer solution or a carbonate buffer solution, is used. The organic solvent as the composition medium is preferably an organic solvent miscible with water, such as methanol, ethanol or acetone. A mixture of these water-miscible organic solvents and the above-mentioned aqueous medium can be used as the composition medium.

The antibacterial agent of the present invention can be used in combination with other antibacterial agents. The antibacterial agent of the present invention has a very broad antibacterial spectrum, and is effective against fungi such as filamentous fungi (fungi), yeasts such as pathogenic yeasts such as Candida, various bacteria including Gram-positive bacteria and Gram-negative bacteria, and the like. Has antibacterial properties.

For example, as bacteria, Bacillus ( Bac
illus ) bacteria, such as Bacillus subtilis ( B
acillus subtilis ), Bacillus anthracis ;
Mycobacterium , for example Mycobacterium smegmatis ( Mycobac)
terium smegmatis ), Mycobacterium tuberculosis ( Mycobacterium)
tuberculosis ); Mycobacterium kansasi
i), Pseudomonas (Pseudomonas), for example Pseudomonas aeruginosa (Pseudom
onas aeruginosa );

Escherichia
a ), for example Escherichia col
i ); Staphylococcus
us ), for example Staphylococcus aureus ( St
aphylococcus aureus); Streptococcus (Streptococcus), for example Streptococcus pyogenes (Streptococ
cus pyogenes ); Salmonella ( Salmo )
nella ), for example Salmonella paratyphi B ( Sa
lmonella parathyphi B);

Klebsiella , for example Klebsiella
pneumoniae); Proteus (Proteu
s ), for example Proteus bulgaris ( Proteus
vulgaris); Vibrio (Vibrio), for example Vibrio cholera (Vibrio cholera
e); Shigella (Shigella), for example, Shigella flexneri (Shigella flexneri),
Shigella Disenteria ( Shigelladysen)
teriae ) and the like have antibacterial properties.

Further, the antibacterial composition of the present invention comprises a fungus,
For example, Aspergillus (Aspergillus), for example, Aspergillus niger (Aspergillus
niger ), Penicillium ( Penicillu )
m ), Cladosporium
m ), Alternaria ( Aternaria ), Fusarium ( Fusarium ) and the like. In addition, it has antibacterial properties against yeasts such as pathogenic yeasts such as Candida, such as Candida albicans . The antibacterial composition of the present invention further has antibacterial properties against various viruses, and examples of these viruses include human immunodeficiency virus (HIV), flupes virus, hepatitis virus and the like.

Since the antibacterial agent of the present invention exhibits antibacterial properties against a wide range of microorganisms as described above, it can be used, for example, in various spaces of hospitals such as hospital rooms and various medical devices, especially in medical, dental and veterinary medicine. It is useful as a sterilizing and disinfecting agent for the hands of medical workers and the body of the body. The antibacterial agent of the present invention is further useful as a disinfecting / sterilizing / sterilizing agent for sanitary control in factories such as drug factories and pharmacies. The antibacterial agent of the present invention is further useful for sterilizing and disinfecting fiber products such as synthetic fibers and natural fibers, especially against fungi. The antibacterial agent of the present invention is also useful for sterilizing airways and filters of air conditioning equipment, or for sterilizing and disinfecting air by introducing it as a trace amount of particles into an air conditioner, etc. It is useful for sterilization and disinfection depending on the object and method.

The quaternary ammonium salt antibacterial component represented by the formula (I) can be synthesized by a conventional method of organic synthesis, but for many uses, it is industrially required to be produced at a low cost and in a large amount. . For this purpose, for example, it is preferable to manufacture as follows. In the first step, alkyldimethylamine obtained from middle distillate of coconut oil distillate is used as a starting material. The alkyl groups (other than the two methyl groups) in this alkyldimethylamine are primarily mixtures of alkyl groups having 10 to 16 carbon atoms.

Alkylbenzyldimethylammonium chloride is obtained by reacting this with benzyl chloride. This reaction is an exothermic reaction and is carried out for 1 to 2 hours while maintaining the reaction temperature at 80 to 90 ° C by external cooling. The product is cooled to 20-30 ° C, then the temperature is raised to 65-85 ° C and finally cooled again. This gives the alkylbenzyldimethylammonium salt marketed as so-called benzalkonium chloride. Therefore, in the present invention, a commercially available raw material can be used by omitting the first reaction.

The above reaction is carried out using, as starting materials, an alkyldimethylamine whose alkyl component is mainly an n-alkyl (lauryl) having 12 carbon atoms (consisting mainly of lauryldimethylamine) and benzyl alcohol. In this case, a reaction product mainly containing laurylbenzyldimethylammonium chloride is obtained. In this reaction, preferably equimolar amounts of the reactants are dissolved in a lower alcohol such as isopropanol (reactant concentration is preferably 5-10%) and preferably maintained at reflux temperature.

In the second-step reaction, an alkyl group (including a methyl group) in the alkyl (eg, lauryl) dimethylbenzylammonium salt (chloride) obtained by the above-mentioned first-step reaction has a longer alkyl group, For example, by substituting with an alkyl group having 16 to 18 carbon atoms, particularly a cetyl group having 16 carbon atoms, a trialkylbenzylammonium salt mainly containing a dialkylcetylbenzylammonium salt is obtained. This reaction is carried out by reacting the above alkyl (eg lauryl) dimethylbenzyl ammonium salt with the corresponding fatty alcohol to replace the alkyl group on the nitrogen atom.

The reaction is carried out in a reactor with stirring at about 4
It is carried out at a temperature of 0 ° C. for 1 to 2 hours. A nonionic surfactant, especially a polyoxyethylenic surfactant having 5 to 6 oxyethylene units, is used as a catalyst for promoting the reaction. Preferred nonionic surfactants are nonionic ethylene oxide condensates, for example alkyl-containing alkyl groups having 7 to 11 carbon atoms.
It is a polyethoxylated product of phenol and has 9 to 17 ethylene oxide units. Dimethylnonyl polyethoxylate is particularly preferred.

The reaction in the third step is a reaction for converting the anion (Cl ⁻ ) in the product mainly containing chloride of dialkylcetylbenzylammonium produced as described above into the anion composed of three halogens. is there. This reaction is carried out by adding molecular halogen to the reaction mixture. For example, I ₂ Cl ⁻ by adding molecular iodine to a quaternary ammonium salt having Cl ⁻ ions.
Ions are generated. Further, in order to generate an anion (I ₂ I ⁻ ) consisting of three iodines, Cl ⁻ ion may be previously replaced with I ⁻ ion and then molecular iodine I ₂ may be added. The reaction is carried out by acidification in order to tilt the equilibrium of the reaction towards the anion consisting of three halogen atoms. For example, adding orthophosphoric acid to pH 3.0
It is preferable to carry out the reaction as follows.

By the above-mentioned method, a molecular population within the definition of the formula (I) satisfying the conditions (a) and / or (b) of the present invention can be obtained. Furthermore, in addition to the conditions (a) and / or (b) of the present invention, the conditions (c) and / or ( A population of molecules within the definition of formula (I) that satisfies d) is obtained.
A phosphoric ester of formula (III), a polyethanolamine of formula (IV), and a formula (V), which are additional components in the present invention.
Ammonium oxide is a known compound, or can be synthesized by a known method.

To produce the antibacterial composition of the present invention containing additional components, the quaternary ammonium salt of formula (I) may be mixed with the additional components. The antibacterial activity of the antibacterial component represented by formula (I) of the present invention is very low. For example, when orally (?) Administered to mice (?), LD of alkyldimethylbenzylammonium chloride currently used is
LD ₅₀ for the active ingredient of formula (I) against ₅₀ that is 569 mg / kg is 1300 mg / kg.

[0045]

EXAMPLES Next, the present invention will be described more specifically by way of examples. Example 1. Preparation of Quaternary Ammonium Salt of Formula (I) Alkyldimethylamine obtained from middle distillate of coconut oil and benzyl chloride were reacted in equal amounts for 2 hours while keeping the reaction temperature at 85 ° C. by external cooling. . Next, a fatty alcohol mainly consisting of cetyl alcohol was added thereto, and further a nonionic polyoxyethylene surfactant (alkyldimethylaminopolyethoxide (alkyl group C ₉ )) was added thereto and reacted at 45 ° C. for 2 hours. Next, orthophosphoric acid was added thereto to adjust the pH to 3, and then molecular iodine was added to generate I ₂ Cl ⁻ ions.

In the thus obtained quaternary ammonium salt represented by the formula (I), the ratio of molecules having a cetyl group bonded to a nitrogen atom is about 90%, and an alkyl group having 14 carbon atoms bonded to a nitrogen atom. The proportion of molecules with groups is about 50%, the proportion of molecules with benzyl groups attached to the nitrogen atom is about 80%, and the proportion of anions I ₂ Cl ⁻ is about total halogenated anions. It was 70%. Example 2. An antibacterial agent having the composition shown in Table 1 below was prepared.

[0047]

[Table 1]

Next, after culturing the cultured bacterial cells of various bacteria for 42 hours at 37 ° C., the total number of the bacterial cells was examined after contacting the diluted antibacterial agent to a concentration of 2% for 1 minute. The results are shown in Table 2 below.

[0049]

[Table 2]

Example 3. Anti-mold test The test was carried out according to the mold resistance test method of Japanese Industrial Standard JIS Z2911. The ratio of each component is as shown in Table 1. The molds tested are: 1. Cladosporium sp. ( Cladospori
um sp . ) 2. Fusarium sp. ( Fusarium sp .) 3. Penicillium sp. ( Penicillium
sp . ) 4. Alternaria sp. ( Alternaria
sp . ) 5. Aspergillus niger (Aspergillus
niger ) Culture at 27 ° C plus or minus 2 ° C for 1 week, 2 weeks, 3
I did it for a week.

The evaluation method is the following 3 according to JIS standard.
A graded evaluation method was adopted. 1: A state in which more than two-thirds of mold is generated on the sample 2: A state in which mold contamination is two-thirds or less on the sample 3: A state in which no mold contamination is observed on the sample The test results are shown in Table 3. Even at a low concentration, the bactericidal effect against mold was sufficient.

[0052]

[Table 3]

[0053]Example 4. Bactericidal effect on bacterial spores Bacillus sub, a bactericide of the present invention prepared in Example 1
Chiris (Bacillus subtilis)
A comparative test of the bactericidal effect was carried out. In addition,The concentration is 2%
(18-hour culture method). The results are shown in Table 4.

[0054]

[Table 4]

Example 5. This example shows an example of a composition that is effective against endospore-forming Gram-positive bacteria. Composition (wt%) Antibacterial component of Example 1 45% Glycerol 14% Polyoxytylated glyceride of fatty acid 20% Orthophosphoric acid ester 5% Polyoxyethylated amine oxide 14% Buffer solution (pH 8.0) 2%

When the above composition was diluted with water to 2% and brought into contact with the test cells for 1 minute, 2.0 × 10 ⁸ cfu was obtained.
/ Ml of Bacillus subtilis (Bacillus su
btilis ), and 1.0 × 10 ⁸ cfu / ml of Mycobacterium tuberculosis ( Mycobacterium)
ium tuberculosis ) was completely sterilized.

Example 6. An antimicrobial agent of the following composition was prepared that was effective against a wide range of microorganisms. Composition (wt%) Antibacterial component of Example 1 44% Polyethylene glycol 13% Polyoxyethylated amine oxide 15% Polyethoxylated primary alcohol 21% Orthophosphoric acid and its ester 5% Buffer solution (pH 7.0) 2%

Various microorganisms were added to a 2% aqueous solution of the above composition.
The bactericidal effect after contacting for 1 minute was as follows.
3.7 x 10⁸cfu / ml Gram-negative bacterium Pseudomonas
・ Aeruginosa (Pseudomonas aeru
ginosa), 1.0 × 10 ⁸cfu / ml opportunistic infection
Escherichia coli (Escherichia co
li), 1.5 × 10⁸cfu / ml gram-positive bacteria stuff
Irococcus aureus (Staphylococc
us aureus) 1 x 10⁸cfu / ml strep
Tococcus pyogenes (Streptococcus
 pyogenes) 2.6 × 10⁸cfu / ml chiff
Subtilis Salmonella paratyphi A (Salmonella
 parathyphi A),

1.7 × 10⁸cfu / ml Salmonella pa
Ratify B (Salmonella parathyph
i B) 1.9 × 10⁸cfu / ml of the pathogen Klebsiella
・ New monia (Klebsiella pneumo
niae), 1.5 × 10 ⁸cfu / ml proteus
Lugaris (Proteus vulgaris), 1.
9 x 10⁸Cfu / ml Vibrio cholerae of Vibrio cholerae (Vi
brio cholerae), And 4.7 × 10
⁷cfu / ml Shigella flexneri (Shigella
 flexneri), And 7.3 × 10⁷cfu / ml
Shigella Disenteria (Shigella dyse
terrier) Was completely sterilized.

Example 7. The following compositions are particularly useful against fungi. This test was performed according to Japanese Industrial Standard Z2199. The test microorganism was Aspergillus niger ( Asp
ergillus niger ), Penicillium s
p. ( Penicillum sp.), Cladosporium sp ( Cladosporium sp), Alternaria sp ( Alternaria sp), and Fusarium sp. ( Fusarium sp.), Which are fungi that often propagate on surfaces such as walls, air conditioners, converter devices, filters, air passages, synthetic or natural fibers.

Composition (weight ratio) Antibacterial component of Example 1 40% Ethanolamide derived from coconut oil 10% Polyethylene glycol 12% Saturated polyethoxylated alcohol 14% Fatty acid glycerol ester 22% Orthophosphoric acid and its ester 2% The above antibacterial composition Was dissolved in an equal mixture of water and isopropanol to a concentration of 0.1-0.5%. as a result,
The 0.2% solution was shown to have the highest antibacterial activity.

Example 8. The composition of this example is very useful for killing bacteria and mold spores. Composition (wt%) Antibacterial component of Example 1 50% Glycol (pentanediol) 11% Coconut oil-derived ethanolamide 14% Polyethoxylated fatty alcohol 15% Glycerol ester of fatty acid 7% Orthophosphoric acid 3% Antibacterial activity is large at pH Affected, the highest antibacterial activity (against spores) was obtained at pH 3.0-3.6.

Example 9. The composition of this example is particularly preferable for application to the skin, and contains a skin protectant and a moisturizer. Composition (wt%) Antibacterial ingredient of Example 1 40% Sodium lauryl ether sulphate 23% Ethanolamide derived from coconut oil 7% Glycerol ester of fatty acid 12% Alkyldimethylamino oxide 13% Amidobetaine derived from coconut 5% This composition is especially medical It is effective for hand washing of workers and effective for protection from infection. This composition contains a nonionic surfactant in order to familiarize the skin with a rapid bactericidal effect.

Example 10. This example demonstrates a composition useful as an antiviral agent. Composition (wt%) Antibacterial component of Example 1 45% Glycerol 12% Glycerol ester of fatty amine 14% Ethanolamide derived from coconut oil 16% Pentanediol 10% Orthophosphoric acid and ester 3% This composition serves as an antiviral agent. Useful against the human immunodeficiency virus (HIV), 0.
1% diluted solution is 1 × 10 ⁷ virus / ml AI for 30 seconds
It is useful for killing and killing DS pathogens and sterilizing and sterilizing AIDS virus.

Example 11. The compositions of this example are generally for non-absorbable surfaces such as dialysis tubing, endoscopic devices, breathing aids and train tubing, and where sterilization by steam or ethylene oxide is impractical or physiologically undesirable. It is a composition that can be applied. Composition (wt%) Antibacterial component of Example 1 46% Alkyldimethylamino oxide 14% Propylene glycol 16% Glycerol 3% Glycerol ester of fatty acid 11% Orthophosphoric acid and ester 2% Coconut oil derived ethanolamide 8%

The composition is effective against bacteria, fungi, viruses and various spores at concentrations lower than half that of the prior art antibacterial agents. For example, when a 2% dilution of the above composition is contacted with microorganisms for 1 minute, 1.0 × 10 ⁸
cfu / ml Mycobacterium smegmatis ( Myco
bacterium smegmatis), 2.4 ×
10 ⁸ cfu / ml Mycobacterium cansassie ( My
cobacterium kansasii ), 8.0
× 10 ⁸ cfu / ml Saccharomyces cerevisiae ( S
accharomyces cerevisiae ),
1 x 10 ⁸ cfu / ml Candida albicans ( Can
dida albicans ), and 2.5 × 10 ⁷ cf
u / ml Bacillus anthracis
anthracis ) was completely sterilized.

[0067]

EFFECTS OF THE INVENTION The bactericide of the present invention has a very strong bactericidal action and is effective in a short time, and has a long duration. Therefore, viruses, bacteria, bacterial spores, fungi, etc. It effectively suppresses and kills the proliferation of bacteria, so it is suitable for medical sterilization and sterilization, disinfection and sterilization of environments such as factories, air conditioning equipment, filter sterilization and sterilization, and the prevention and prevention of mildew and fungi. It covers a wide range of treatments.

Claims (19)

[Claims] 1. The following general formula (I): [In the formula, R ₁ is an alkyl group having 6 to 18 carbon atoms or a benzyl group; R ₂ is a hydrogen atom, 1 to 1 carbon atoms.
An alkyl group having 8 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, or an aralkyl group; R ₃ has 12 to 12 carbon atoms;
22 alkyl groups; R ₄ has 8 to 18 carbon atoms
Alkyl groups or the following formula (II): (Wherein R ₅ is an alkyl group having 2 to 22 carbon atoms, and n is 2 or 3); and Y is an anion composed of 1 or 3 halogen atoms. In the antibacterial agent comprising a plurality of molecular species defined by the following conditions, (a) the ratio of the number of molecules having an alkyl group having 16 carbon atoms as R ₃ is all within the above definition. 80 for the number of molecules
% Or more; (b) of the monovalent anions defined as Y, the ratio of anions consisting of three halogen atoms is 50% or more with respect to the number of anions within the definition of Y above; An antibacterial agent characterized by satisfying (a) or (b), or both (a) and (b). 2. The above condition: (a) or (b), or both of (a) and (b) are satisfied, and the following condition (c) is a ratio of the number of molecules having a benzyl group as R ₁ .
70% or more with respect to the number of molecules within the above definition; (d) The ratio of the number of molecules having an alkyl group with 14 to 16 carbon atoms as R ₂ is 40% with respect to the number of molecules within the above definition. It is above; Among them, (c) or (d), or both (c) and (d) are satisfy | filled, The antibacterial agent of Claim 1 characterized by the above-mentioned. 3. The antibacterial agent according to claim 1, which satisfies all the conditions (a), (b), (c) and (d). 4. The definition relating to formula (I) above, wherein the ratio of the number of molecules having an alkyl group having 16 carbon atoms as (a ′) R _{3 to} the total number of molecules within the above definition is 9
0% or more; (b ') The proportion of anions consisting of three halogen atoms among the monovalent anions defined as Y is 70% with respect to the anions within the definition of Y; The antibacterial agent according to any one of claims 1 to 3, wherein (a ') or (b') or both (a ') and (b') are satisfied. 5. In the definition of (I) above, the above condition: (a ′) or (b ′), or both of (a ′) and (b ′) are satisfied, and the following condition: (c ′) ) The ratio of the number of molecules having a benzyl group as R ₁ is 80% or more with respect to the number of molecules within the above definition; (d ′) The number of molecules having an alkyl group having 14 to 16 carbon atoms as R ₂ The ratio is 50% or more with respect to the number of molecules within the above definition; in (c ′) or (d ′),
Alternatively, the antibacterial agent according to any one of claims 1 to 4, which satisfies both of (c ') and (d'). 6. The conditions (a ′), (b ′),
The antibacterial agent according to any one of claims 1 to 5, which satisfies all of (c ') and (d'). 7. As an additional component, (1) the following formula (III): (In the formula, the sum of x and y is 3, and R ₆ has 3 carbon atoms.
To 20 organic groups and p is 1 to 2); (2) the following formula (IV): (In the formula, z is an integer of 2 to 10 and R ₇ is an alkyl group having 2 to 22 carbon atoms); (3) The following formula (V): 5] The ammonium oxide represented by the formula (wherein R ₈ is an alkyl group having 4 to 18 carbon atoms), further comprising at least one member selected from the group consisting of: Antibacterial agent. 8. The total amount of one or more additional components is 30 to 10 parts by weight based on 70 to 90 parts by weight of the quaternary ammonium salt represented by the formula (I). Antibacterial agent. 9. When 70 to 90 parts by weight of the quaternary ammonium salt represented by the formula (I) is used, the amount of the surface active phosphate ester (1) of the formula (III) is 3 to 7 parts by weight. Parts when the polyethanolamine of the formula (IV) is used, the amount is 5 to 15 parts by weight, and when the ammonium oxide of the formula (V) is used, the amount is 5 to 10 parts by weight.
The antibacterial agent according to claim 8, which is parts by weight. 10. In addition to the quaternary ammonium salt of formula (I), it contains all additional components of formula (III) to formula (V),
The antibacterial agent according to any one of claims 8 and 9. 11. In addition to the quaternary ammonium salt of the formula (I), it comprises all the additional components of the formulas (III) to (V), the amount of which relative to the total amount of the quaternary ammonium salt of the formula (I) is: 68 to 72 parts by weight of a quaternary ammonium salt having an anion consisting of 3 halogen atoms, and 6 to 6 parts of a quaternary ammonium salt of the formula (I) having an anion consisting of a halogen atom. 10 parts by weight, 3 to 7 parts by weight of the phosphoric acid ester of the formula (III), 8 to 12 parts by weight of the polyethanolamine of the formula (IV), and 5 to 9 parts of the ammonium oxide of the formula (V). The antibacterial agent according to any one of claims 6 to 10, which is parts by weight. 12. In addition to the quaternary ammonium salt of the formula (I), it comprises all the additional components of the formula (III) to the formula (V), the amount of the formula (I) being approximately as a whole.
70 parts by weight of the quaternary ammonium salt having 3 anions of halogen atom, and 8 parts of the quaternary ammonium salt of formula (I) having 1 anion of halogen atom. Parts, 5 parts by weight of the phosphoric acid ester of the formula (III) and 10 parts by weight of the polyethanolamine of the formula (IV).
The antibacterial agent according to claim 11, wherein the parts by weight and the amount of the ammonium oxide of the formula (V) are 8 parts by weight. 13. The amount of the quaternary ammonium salt represented by the formula (I), or 1 to 1 in addition to the quaternary ammonium salt of the formula (I).
When a plurality of additional components of formulas (III) to (V) are included, the total amount thereof is 0.0001 to 1 with respect to the entire antibacterial composition.
The antibacterial composition according to any one of claims 1 to 12, which is 00% by weight. 14. The antibacterial agent according to claim 1, wherein the bactericidal component is dissolved in water or an organic solvent. 15. The disinfection / sterilization / sterilization of bacteria, bacterial spores, fungi and viruses on the surface of a human body or an object, the sterilization / sterilization agent according to any one of claims 1 to 14 alone or together with other disinfectants. Sterilization and sterilization method using the sterilizing agent used for. 16. The sterilization / sterilization method according to claim 15, wherein the disinfection / sterilization / sterilization is performed in a hospital, factory, drug factory, or pharmacy. 17. A sterilizing method using the sterilizing agent according to claim 1 for sterilizing and sterilizing an air conditioner and a filter. 18. A method of using a disinfectant for use in disinfecting or sterilizing a surface of an instrument or instrument in the field of medical, dental or veterinary medicine, wherein the disinfectant or sterilizer according to any one of claims 1 to 14 is used. 19. The fungicide according to any one of claims 1 to 14 against fungi on the surface of a human body, a plant or an object.
And a method of using a bactericide for sterilizing or disinfecting fungi on the surface of synthetic fiber or natural fiber cloth and other substances.