JP2877727B2 - Disinfecting and disinfecting detergent having chelating ability and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disinfectant detergent having a chelating ability and a method for producing the same. The germicidal disinfectant cleaning agent of the present invention is particularly useful for germicidal disinfection for medical treatment requiring germicidal disinfection or germicidal disinfection, disinfection and disinfection for food factory equipment, germicidal disinfection for the environment, or cleaning thereof.

[0002]

2. Description of the Related Art In the case of using a disinfectant, it is necessary to determine a concentration sufficient for microorganisms having the least disinfecting effect to exert their disinfecting effect. Conventionally used cationic disinfectants may have different disinfecting efficiencies depending on the type of microorganism, and in particular, some pseudomonas (Pseudomonmon).
as) The bactericidal effect against the genus Bacteria is larger than other microorganisms, and the bactericidal effect is low.
It was necessary to use a high concentration for sterilization and disinfection for food factories and the environment. However, when the use concentration is increased, various problems such as causing skin irritation and accelerating corrosion of instruments and the like occur. Further, in order to impart detergency, it is necessary to use a nonionic surfactant in combination, and there is a contradiction that the sterilization effect is reduced when the nonionic surfactant is used in combination.

[0003]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the conventional disinfectants by providing a high germicidal effect even at a low concentration, and has an excellent detergency, and is therefore suitable for the human body. Provide a sterilizing and disinfecting detergent suitable as a sterilizing and disinfecting agent for medical use, a disinfecting agent for dental use, a disinfecting agent for food factories, an disinfecting agent for environment, etc. The purpose is to:

[0004]

The present inventors have conducted intensive studies to develop a germicidal detergent having the above-mentioned preferable properties. As a result, a specific cationic germicidal disinfectant detergent compound having chelating ability has been obtained. It has a germicidal effect stronger than the germicidal effect obtained by conventional cationic disinfectants, and also has a detergency, so it should be used at a low concentration that does not affect the human body or corrode metal appliances. Have been found possible, and the present invention has been completed.

That is, according to the present invention, one or two quaternary ammonium salts represented by the following general formula (1) are provided.
A germicidal disinfecting detergent having chelating ability comprising at least one species is provided.

[0006]

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Wherein R ¹ represents an alkyl or alkenyl group having 10 to 18 carbon atoms, R ² represents a hydrogen atom, a methyl group or a phenoxymethyl group, n is an integer of 1 to 3, and m is X ^m- represents an anion from an aminocarboxylic acid represented by the following general formula (2), and when a plurality of R ¹ and R ² are present, they are the same. Or may be different)

[0008]

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(Wherein M represents a hydrogen atom or an alkali metal atom, and R ³ and R ⁴ are each independently —CH ₂
A COOM group, a hydroxyethyl group or a group represented by the following general formula (3))

[0010]

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(Wherein M independently represents a hydrogen atom or an alkali metal atom) The quaternary ammonium salt represented by the general formula (1) is
According to the present invention, a tertiary amine salt obtained by reacting an amine compound represented by the following general formula (4) with an aminocarboxylic acid represented by the above general formula (2) is added to a tertiary amine salt represented by the following general formula (5)
Can be produced by reacting an epoxy compound represented by

[0012]

Embedded image

(Wherein, R ¹ represents an alkyl or alkenyl group having 10 to 18 carbon atoms)

[0014]

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(Wherein R ⁵ represents a hydrogen atom, a methyl group or a phenoxymethyl group) Examples of the amine compound represented by the general formula (4) include decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, and hexadecyldimethylamine. Examples include alkyldimethylamines such as decyldimethylamine and octadecyldimethylamine. These may be used alone or in a mixture. Of these compounds, dodecyldimethylamine, tetradecyldimethylamine and hexadecyldimethylamine are preferred.

As the aminocarboxylic acid represented by the general formula (2), nitrilotriacetic acid, nitrilotriacetic acid monometal salt,
Nitrilotriacetic acid dimetallic salt, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid monometallic salt, ethylenediaminetetraacetic acid dimetallic salt, ethylenediaminetetraacetic acid trimetallic salt, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid monometallic salt, diethylenetriaminepentaacetic acid dimetallic salt, Examples thereof include trimetal salts of diethylenetriaminepentaacetic acid and tetrametal salts of diethylenetriaminepentaacetic acid. Of these,
Nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are preferably used.

As the epoxy compound represented by the general formula (5), ethylene oxide, propylene oxide and phenylglycidyl ether are suitably used, and the reaction molar ratio is 1 to 2 times, preferably 1 to 2 times, the mole of the tertiary amine salt. Is preferably 1 to 1.5 times mol. When the molar ratio is more than twice, the bactericidal effect is reduced, but the detergency is higher than that of an anionic surfactant such as sodium lauryl sulfate which has been conventionally used as a detergent. The reaction conditions are not particularly limited, but water or a mixed solvent of alcohol and water is suitable as the reaction solvent, and the reaction temperature is preferably 50 to 100 ° C.

The quaternary ammonium salt of the general formula (1) obtained by this reaction includes, for example, alkyl hydroxyethyl dimethyl ammonium salt (AHEDMA) and alkyl hydroxypropyl dimethyl ammonium salt (AH
PDMA), alkyl-2-hydroxy-3-phenoxypropyldimethylammonium salt and the like.
Examples of the alkyl group of these compounds include a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and the like, and they may be used alone or in a mixture. Particularly preferably, in the quaternized product of ethylene oxide and propylene oxide, the alkyl group is a single or mixture of dodecyl group, tetradecyl group and hexadecyl group. In the quaternized product of phenylglycidyl ether, the alkyl group is dodecyl group and tetradecyl group. It may be a single or a mixture of groups.

The germicidal cleaning agent of the present invention is soluble in water, and is usually conveniently used as an aqueous liquid containing it. When such an aqueous liquid is used as a disinfectant, the concentration of the compound of the general formula (1) is 0.05 to 0.2.
The compound is preferably used at a concentration of 0.1 to 0.5% by weight, and when used as a germicidal detergent, the compound of formula (1) is preferably used at a concentration of 0.1 to 0.5% by weight. In addition, such aqueous liquids include solvents such as ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol, and nonionic surfactants for improving detergency. It can be used together in a range that does not exist.

[0020]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" are parts by weight. The method for measuring the bactericidal effect based on the concentration of the disinfectant and the contact time with the bacterial solution was used for evaluating the bactericidal efficacy of the germicidal disinfecting detergent, and the test method for removing collagen hydrolyzate derivatives was used for evaluating the detergency.

Disinfectant Concentration-Sterilization Effect by Bacterial Solution Contact Time
Measurement of four types of hospital clinical isolates, namely E. coli N
o.94211), K. pneumoniae
No. 94311), Pseudomonas aeruginosa (P. aeruginosa)
No. 94411) and S. marcescen.
s No. 94511) was inoculated into a BHI liquid medium at 33 ° C.
For 24 hours with shaking. 0.05 ml of the bacterial solution adjusted to 10 ⁸ cfu / ml was added to 5 ml of a 10-fold dilution line of a sterilizing / disinfecting detergent solution, and allowed to contact for 5 or 10 minutes. Ear applied, 48 at 30 ° C
The cells were cultured for a period of time to determine whether or not the bacteria had grown.

The judgment of the effect was based on the following criteria. -: bacteria killed (there bactericidal effect) +: is found only 10 or less growth colonies of bacteria (there bactericidal effect considerably) ++: Growth of bacteria found in coating the entire surface (no bactericidal effect) Collagen hydrolyzate non-aqueous contamination solution consisting monooleate removal test method collagen hydrolyzate hydrolyzate derivative and liquid paraffin (hereinafter referred to as "CMO")
Place 0.05 ml on a 2 cm x 2 cm square stainless steel plate.
Bake at 50 ° C. for 2 hours. This plate is immersed in 40 ml of a sample solution adjusted to a concentration of 0.2%, allowed to stand for 30 minutes, and then lightly rinsed with running water.

The cleaning criteria were determined according to the following criteria. ：: The CMO film did not remain on the metal plate at all, and was completely removed. ：: The CMO film remained very slightly on the metal plate. X: A large amount of the film remained on the metal plate. Ethylenediaminetetraacetic acid (hereinafter abbreviated as "TAA") 2
9.2 parts and 220 parts of water were charged into a reaction vessel, and alkyldimethylamine (the alkyl group was a dodecyl group,
A mixture of tetradecyl and hexadecyl groups,
The average formula of the mixture is C ₁₃ H ₂₇ (hereinafter “ADMA”).
23.0 parts are added for neutralization. Next, 6 parts of ethylene oxide was added thereto, reacted at 80 ° C. for 3 hours, steam-distilled, and then adjusted to a concentration of 10% with water.

Example 2 A reaction vessel was charged with 29.2 parts of TAA and 350 parts of water, and neutralized by adding 46.0 parts of ADMA thereto. Next, 12 parts of ethylene oxide was charged into this,
After reacting at 3 ° C. for 3 hours and performing steam distillation, the concentration was adjusted to 10% with water.

Example 3 A reaction vessel was charged with 29.2 parts of TAA and 110 parts of water, and 69.0 parts of ADMA was added to neutralize the reaction vessel. Then, 18 parts of ethylene oxide was charged into the
After reacting at 3 ° C. for 3 hours and performing steam distillation, the concentration was adjusted to 10% with water.

Example 4 A reaction vessel was charged with 29.2 parts of TAA and 540 parts of water, and 69.0 parts of ADMA was added to neutralize the reaction vessel. Next, 36 parts of ethylene oxide was charged into this,
After reacting at 3 ° C. for 3 hours and performing steam distillation, the concentration was adjusted to 10% with water.

Example 5 A reaction vessel was charged with 29.2 parts of TAA and 480 parts of water, and 69.0 parts of ADMA was added to neutralize the reaction vessel. Next, 23 parts of propylene oxide was charged into this,
After reacting at 0 ° C. for 3 hours and performing steam distillation, the concentration was adjusted to 10% with water.

Example 6 A reaction vessel was charged with 29.2 parts of TAA and 570 parts of water, and 69.0 parts of ADMA was added to neutralize the reaction vessel. Next, 45 parts of phenylglycidyl ether was charged into the mixture, reacted at 100 ° C. for 3 hours, and subjected to steam distillation.
The concentration was adjusted to 10% with water.

Example 7 A reaction vessel was charged with 39.3 parts of diethylenetriaminepentaacetic acid (hereinafter abbreviated as "DTPA") and 300 parts of water.
69.0 parts of ADMA is added thereto for neutralization. Next, 18 parts of ethylene oxide was charged into this,
For 3 hours, and after steam distillation, the concentration was adjusted to 10% with water.

Example 8 Ethylenediaminehydroxyethyltriacetic acid (hereinafter referred to as "HE
27.8 parts and 220 parts of water are charged into a reaction vessel, and 46.0 parts of ADMA is added thereto to neutralize. Next, 12 parts of ethylene oxide was added thereto, reacted at 80 ° C. for 3 hours, steam-distilled, and the concentration was adjusted to 10% with water.

Comparative Example 1 28.6 parts of an alkyl phosphate ester synthesized from 3 mol of n-butanol and 1 mol of phosphoric anhydride and having a mixing ratio of mono / di 50/50 and 100 parts of water were placed in a reaction vessel. Charge and add 46 parts of ADMA to neutralize. Next, 13 parts of ethylene oxide was added thereto, reacted at 100 ° C. for 3 hours, steam distilled, and the concentration was adjusted to 10% with water.

Comparative Example 2 A reaction vessel was charged with 23.6 parts of fumaric acid and 100 parts of water.
Neutralize by adding 46 parts of ADMA. Next, 13 parts of ethylene oxide was added thereto, reacted at 100 ° C. for 3 hours, steam distilled, and the concentration was adjusted to 10% with water. Test Example 1 The compounds of Examples 1 to 8 and Comparative Examples 1 and 2 were subjected to an antibacterial test against four types of clinically isolated bacteria in a hospital in accordance with "Disinfectant concentration-Method of measuring bactericidal effect by contact time with bacterial solution". The results shown in Tables 1 to 4 were obtained.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

Test Example 2 Compounds of Examples 1 to 8 and Comparative Examples 1 and 2, and sodium lauryl sulfate as a comparative product (Comparative Example 3)
, And a detergency test was carried out according to "Testing method for removing collagen hydrolyzate derivative". Table 5 shows the results.

[0038]

[Table 5]

From the above results, the quaternary ammonium salts having these chelate-forming compounds as counter ions (Examples 1 to 8) are the quaternary ammonium salts having compounds having no chelate-forming ability as counter ions. Ammonium salts, for example, a quaternary ammonium salt in which the counter ion of the general formula (1) is replaced with a phosphate ester (Comparative Example 1) and a quaternary ammonium salt in which the counter ion is replaced by a polyvalent carboxylic acid, fumaric acid Compared with (Comparative Example 2), it is superior in bactericidal efficacy. Also, it can be seen that the removability of the water-insoluble protein derivative contaminated liquid is very good even compared to sodium lauryl sulfate (Comparative Example 3).

[0040]

Industrial Applicability The cationic germicidal disinfectant cleaning agent of the present invention comprises:
Because of its excellent sterilizing effect and extremely high cleaning effect, it is possible to lower the concentration of the sterilizing / cleaning agent used compared with the conventional one, and it can be expected that the effect on the human body is reduced. Furthermore, since it has a large cleaning effect on metals, it can be used for sterilizing cleaning of medical equipment and utensils, machinery of food factories, etc. and for sterilizing cleaning of the environment.

Claims (2)

(57) [Claims] 1. A germicidal and disinfecting detergent having chelating ability, comprising one or more quaternary ammonium salts represented by the following general formula (1). Embedded image (Wherein, R ¹ represents an alkyl or alkenyl group having 10 to 18 carbon atoms, R ² represents a hydrogen atom, a methyl group or a phenoxymethyl group, n is an integer of 1 to 3, and m is 1 to 5 X ^m- represents an anion derived from an aminocarboxylic acid represented by the following general formula (2). When a plurality of R ¹ and R ² are present, they are the same, May also be different). (Wherein, M represents a hydrogen atom or an alkali metal atom,
R ³ and R ⁴ each independently represent a —CH ₂ COOM group,
Represents a hydroxyethyl group or a group represented by the following general formula (3): (Wherein, M independently represents a hydrogen atom or an alkali metal atom) 2. In producing the germicidal disinfectant according to claim 1, an amine compound represented by the following general formula (4) and an aminocarboxylic acid represented by the following general formula (2): Is reacted with an epoxy compound represented by the following general formula (5) to obtain a quaternary ammonium salt represented by the general formula (1) according to claim 1. A method that includes Embedded image (In the formula, R ¹ represents an alkyl or alkenyl group having 10 to 18 carbon atoms.) (Wherein, R ⁵ represents a hydrogen atom, a methyl group or a phenoxymethyl group)