JPH04316503A - Antimicrobial agent - Google Patents

Abstract

PURPOSE:To provide an antimicrobial agent having a high antimicrobial activity, substantially not corroding metal equipment, apparatuses, etc., not causing the deterioration of the antimicrobial activity because of not forming an insoluble complex even when mixed with an anionic surfactant, and suitable as a disinfectant for medical treatments, an environmental disinfectant, an antimicrobial agent for fibers, etc. CONSTITUTION:An antimicrobial agent contains one kind or more of compounds selected from quaternary ammonium salts of the formula (R<1> is 8-22C alkyl or alkenyl; R<2> is 1-22C alkyl or alkenyl; R<3> is 1-5C alkyl; R<4> is alkylene; Ar is substitutable aryl or heteroaryl; X<m-> is alkyl phosphate ion, polyoxyalkylene alkyl ether phosphate ion; m is 1,2; n is 1-5). The antimicrobial agent has an excellent antimicrobial activity and further excellent corrosion-resistant property and compatibility with anionic surfactants.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fungicide, and more particularly to a fungicide comprising a quaternary ammonium salt having fungicidal activity in place of benzalkonium chloride.

0002

[Prior Art] Conventionally, quaternary ammonium salts and amphoteric surfactants, such as benzalkonium chloride and alkyldiaminoglycine hydrochloride, have been used as disinfectants and are relatively safe for the human body and have good properties. It is widely used because it has bactericidal activity. However, these quaternary ammonium salts and amphoteric surfactants corrode metal equipment and instruments, and when mixed with anionic surfactants, they form insoluble complexes, reducing bactericidal activity. are doing. When benzalkonium chloride is used as a sterilizing disinfectant, its use is inevitably limited due to the above-mentioned drawbacks, and benzalkonium chloride is also used to sterilize dental medical instruments. In some cases, sodium nitrite is usually used in combination to prevent rust on the equipment. However, the combination with sodium nitrite has the problem of carcinogenicity due to nitrosation, and cannot be said to be a preferred method of use.

0003

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional disinfectants made of quaternary ammonium salts and amphoteric surfactants, has high bactericidal activity, and is suitable for use in metal equipment and utensils. In addition to having low corrosiveness against substances such as bacteria, it does not form an insoluble complex even when anionic surfactants are mixed in, and the bactericidal activity does not decrease, making it suitable for use as, for example, medical disinfectants, environmental disinfectants, textile disinfectants, etc. It was developed with the aim of providing a disinfectant.

0004

[Means for Solving the Problems] As a result of intensive research to develop a disinfectant having the above-mentioned preferable properties, the present inventors have found that quaternary ammonium salts, which generally have disinfectant properties such as benzalkonium chloride, have been developed. The counter ion is a halogen ion, which is the cause of rust, and the formation of an insoluble complex with an anionic surfactant is caused not only by the cation component but also by the anion of the counter ion. Focusing on the fact that the bactericidal power largely depends on the structure of the cationic component, we used an organic anion with anti-corrosion and buffering ability instead of an inorganic ion as a counter ion, and added nitrogen atoms to maintain or improve the bactericidal power. It has been discovered that the objective can be achieved by a quaternary ammonium salt in which an aralkyl group is introduced into a quaternary ammonium salt, and based on this knowledge, the present invention has been completed. That is, the present invention provides the general formula

[0005]

[Case 2]

(In the formula, R1 is an alkyl group or alkenyl group having 8 to 22 carbon atoms, R2 is an alkyl group or alkenyl group having 1 to 22 carbon atoms, R3 is an alkyl group having 1 to 5 carbon atoms, and R4 is an alkylene group. , Ar is an aryl group or heteroaryl group with or without a substituent, Xm- is an alkyl phosphate ion or a polyoxyalkylene alkyl ether phosphate ion, m is 1 or 2
, n is an integer of 1 to 5). The present invention will be explained in detail below.

Xm- in the general formula [1] is an alkyl phosphate ion or a polyoxyalkylene alkyl ether phosphate ion, and the formation of this ion is performed according to the general formula

[0008]

[Chemical formula 3]

[In the formula, R5 is an alkyl group or alkenyl group having 1 to 22 carbon atoms, R6 is an alkylene group having 2 to 4 carbon atoms, a is 0 or an integer of 1 to 10, and b is 1 (phosphoric acid monoester ) or 2 (phosphoric acid diester)] and polyoxyalkylene alkyl ether phosphoric esters are used.

In the quaternary ammonium salt of the present invention, in order to improve the bactericidal activity, an aryl group or hetero- It is necessary to introduce an oxyalkylene group with an aryl group. To introduce such an oxyalkylene group, for example, an epoxy compound having an aryl group or a heteroaryl group is preferably used. Representative examples of the epoxy compound include phenylglycidyl ether, styrene oxide, and 8-quinolylglycidyl ether.

[0011] Examples of the mono-long chain alkyldilower alkylamine include octyldimethylamine, octyldiethylamine, decyldimethylamine, decyldiethylamine, lauryldimethylamine, lauryldiethylamine, myristyldimethylamine, myristyldiethylamine, palmityldimethylamine, Examples include palmityl diethylamine, stearyldimethylamine, stearyldiethylamine, oleyldimethylamine, oleyldiethylamine, and the like. On the other hand, the di-long chain alkyl mono-lower alkylamines include, for example, dioctylmethylamine, dioctylethylamine, didecylmethylamine, didecylethylamine, dilaurylmethylamine, dilaurylethylamine, dimyristylmethylamine, dimyristylethylamine, dipal Examples include mitylmethylamine, dipalmitylethylamine, distearylmethylamine, distearylethylamine, dioleylmethylamine, and dioleylethylamine.

There are no particular restrictions on the method for producing the quaternary ammonium salt represented by the general formula [1], and conventionally known methods can be used. For example, the mono-long chain alkyl di-lower alkylamine or the di-long chain alkyl mono-lower alkyl amine is neutralized by adding a neutralizing equivalent amount of the phosphoric acid monoester and/or phosphoric diester represented by the general formula [2]. , after making an aqueous solution, this is usually 50~
By heating to a temperature of 150° C., preferably around 100° C., then adding the epoxy compound to this aqueous solution at a ratio of 1 to 5 times the mole, preferably 1 to 2 times the mole of the amine, and reacting. The desired quaternary ammonium salt is obtained. The quaternary ammonium salt of the present invention thus obtained has not only excellent bactericidal activity but also excellent rust prevention and compatibility with anionic surfactants, and can be used for various purposes as a bactericidal agent. be able to.

[0013]

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way. The performance of the disinfectant was evaluated as follows. (1) Rust prevention: Spread 4 layers of gauze in a 9cm diameter petri dish.
Add 10 ml of a 1 wt % aqueous solution of a disinfectant to this so that the gauze is fully immersed in the liquid. Next, 10 acetone-cleaned insect pins were placed on top of the pins and left in contact at 45°C for 48 hours, after which the number of rusted pins was expressed as a percentage. (2) Klebsiella pneumonia as a bactericidal test bacterium
iae IFO-13277 was used. The test method used the commonly used liquid medium dilution method to examine the effectiveness of the disinfectant depending on the contact time with the bacteria, and according to the following criteria,
We looked for bactericidal properties. Judgment criteria -: No growth of bacteria is observed. +: Growth of bacteria is observed. (3) Compatible bactericidal agent with anionic surfactant 1wt%
The compatibility between the aqueous solution and a 1 wt% aqueous solution of anionic surfactant was determined.

Example 1 24 parts by weight of methyl phosphoric acid ester obtained from 10 parts by weight of methyl alcohol and 14 parts by weight of phosphoric anhydride and 14 parts by weight of water
Charge 6 parts by weight of lauryldimethylamine into a reactor, and add 3 parts by weight of lauryl dimethylamine
After neutralizing by adding 4 parts by weight, 15 parts by weight of phenylglycidyl ether was added thereto and reacted at 100°C for 3 hours to obtain the fungicide (1) of the present invention.

Example 2 28 parts by weight of ethyl phosphate obtained from 14 parts by weight of ethyl alcohol and 14 parts by weight of phosphoric anhydride and 15 parts by weight of water.
Charge 4 parts by weight of lauryldimethylamine into a reactor and add 3 parts by weight of lauryldimethylamine.
After neutralizing by adding 4 parts by weight, 15 parts by weight of phenyl glycidyl ether was added thereto and reacted at 100°C for 3 hours to obtain the fungicide (2) of the present invention.

Example 3 32 parts by weight of isopropyl phosphate obtained from 18 parts by weight of isopropyl alcohol and 14 parts by weight of phosphoric anhydride and 162 parts by weight of water were charged into a reactor, and 34 parts by weight of lauryldimethylamine was added. After neutralization, 60 parts by weight of phenylglycidyl ether was added to it, and 100 parts by weight
The fungicide (3) of the present invention was obtained by reacting at ℃ for 3 hours.

Example 4 36 parts by weight of butyl phosphoric acid ester obtained from 22 parts by weight of butyl alcohol and 14 parts by weight of phosphoric anhydride and 17 parts by weight of water.
0 parts by weight of lauryldimethylamine were charged into the reactor, and lauryldimethylamine 3
After neutralizing by adding 4 parts by weight, 15 parts by weight of phenyl glycidyl ether was added thereto, and the mixture was reacted at 100°C for 3 hours to obtain the fungicide (4) of the present invention.

Example 5 41 parts by weight of ethoxyethyl phosphate obtained from 27 parts by weight of ethyl cellosolve and 14 parts by weight of phosphoric acid anhydride and 180 parts by weight of water were charged into a reactor, and 34 parts by weight of lauryldimethylamine was added. After neutralization, 15 parts by weight of phenylglycidyl ether was added thereto, and the mixture was reacted at 100° C. for 3 hours to obtain the fungicide (5) of the present invention.

Example 6 28 parts by weight of ethyl phosphate obtained from 14 parts by weight of ethyl alcohol and 14 parts by weight of phosphoric anhydride and 74 parts by weight of water
Charge parts by weight into a reactor and add 34 parts by weight of lauryldimethylamine.
After neutralizing by adding parts by weight, 12 parts by weight of styrene oxide was added thereto, and the mixture was reacted at 100° C. for 3 hours to obtain the fungicide (6) of the present invention.

Example 7 28 parts by weight of ethyl phosphoric acid ester obtained from 14 parts by weight of ethyl alcohol and 14 parts by weight of phosphoric anhydride and 81 parts by weight of water.
Charge parts by weight into a reactor and add 38% of dioctylmethylamine.
After neutralizing by adding parts by weight, 15 parts by weight of phenyl glycidyl ether was added thereto, and the mixture was reacted at 100° C. for 3 hours to obtain the fungicide (7) of the present invention.

Example 8 28 parts by weight of ethyl phosphate obtained from 14 parts by weight of ethyl alcohol and 14 parts by weight of phosphoric anhydride and 72 parts by weight of water.
Charge parts by weight into a reactor, and add 24 parts by weight of octyldimethylamine.
After neutralizing by adding parts by weight, 20 parts by weight of 8-quinolyl glycidyl ether was added thereto, and the mixture was reacted at 100°C for 3 hours to obtain the fungicide (8) of the present invention.

Test Example 1 The fungicide and benzalkonium chloride of the present invention obtained in Examples 1 to 8 were evaluated for their bactericidal properties, rust prevention properties, and compatibility with the anionic surfactant ABSNa (sodium alkylbenzenesulfonate). I asked for The results are shown in Table 1.

[0023]

[Table 1]

[0024]

Effects of the Invention The disinfectant of the present invention overcomes the drawbacks of conventional disinfectants comprising quaternary ammonium salts and amphoteric surfactants.
In other words, (1) causing rust on metal such as medical instruments;
(2) forming an insoluble salt with an anionic surfactant;
In addition to eliminating the two major drawbacks of reduced bactericidal activity, it also has higher bactericidal activity against Gram-negative bacteria than benzalkonium chloride, and is useful for example in medical disinfectants, environmental disinfectants, and textiles. It is suitable for use as a disinfectant.

Claims (1)

[Claims] Claim 1: General formula [Formula 1] (In the formula, R1 is an alkyl group or alkenyl group having 8 to 22 carbon atoms, R2 is an alkyl group or alkenyl group having 1 to 22 carbon atoms, and R3 is an alkyl group or alkenyl group having 1 to 5 carbon atoms. R4 is an alkylene group, Ar is an aryl group or heteroaryl group with or without a substituent, Xm- is an alkyl phosphate ion or a polyoxyalkylene alkyl ether phosphate ion, m is 1 or 2, n is 1 to 5
A disinfectant comprising at least one kind selected from quaternary ammonium salts represented by (an integer of ).