IL31347A - Washing and cleaning agents and their use - Google Patents

Description

ona mn*tfni np*3i nst*m »y»0K Washing and cleaning agents and their use CIBA-GEIGY Α·0. Οϊ 29623 The present invention relates to_ washing and cleaning agents which contain as active component at least one car-banilic acid derivative of the general formula (I) in which R^ represents hydrogen, halogen, lower . alk l , lower alkoxy, acyl, CN, N02 or CF^, Rg stands for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN or 02, R^ for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN, 02 or CF^, and B for a branched, saturated or unsaturated aliphatic radical or a linear, unsaturated aliphatic radical containing 5 to 12 carbon atoms which may be interrupted by one or several oxygen and/or sulfur atoms, or R stands for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN, 0≥ or CP^, R2 for hydrogen, bromine, lower alkyl, lower alkoxy, acyl, CN or N02, R^ · for hydrogen, lower alkyl, lower alkoxy, acyl, CN, 02 or CF^ ' and B for a linear, saturated or unsaturated aliphatic radical containing 5 to 12 carbon atoms which may be interrupted by one or several oxygen and/or sulfur atoms, at least one of the substituents R^, Rg and R^ being different from hydrogen, and Y stands for an oxygen or sulfur atom or the NH group.

This invention also relates to the use of a washing or cleaning agent as defined above for the biocidal 'dressing of textile and non-textile fiber materials and flat structures.

The lower alkyl and alkoxy radicals comprised by the de and are preferably methyl or ethyl radicals. By halogen, F, CI, Br or I are intended, preferably CI or Br. The acyl radicals mentioned may be of organic or inorganic origin; they may be for example radicals of sulfuric or phosphoric acid substituted by lower aliphatic radicals, preferably lower alkyl radicals or amino groups, and also radicals of lower aliphatic carboxylic acids. The CF^ group may be mentioned as a further substituent for R1 and R . It goes without saying that other halogenalkyl groups, as for example the CHFg, CHgP, ■Cci CHClg, CHgCl, CClgF or CC1F2 group are likewise suitable When the halogenalkyl group is not CF , then R≥ may be a halogenalkyl group. Special mention is deserved by compounds-which contain two CF^ group, that is to say, in which R≥ represents hydrogen, and R^ and R^ each represents a CF^ group. Depending on the substituent R^, B represents a branched or linear, saturated' or unsaturated aliphatic . radical which may be interrupted by one or several oxygen and/or sulfur atoms. Aliphatic radicals having 5 to 10 carbon atoms lead to particu larly valuable compounds. Such aliphatic radicals may be in particular alkyl, alkenyl or alkinyl radicals. Examples of such radicals are inter alia: n-propyl, isopropyl-, n-butyl, secondary butyl, isobutyl, tertiary butyl, amyl, isoamyl, neopentyl, a,7-dimethy.lpentyl , n-hexyl, 2-ethyl -hexyl., iso-hexyl, or n-heptyl, n-octyl, tertiary octyl, n-nonyl, i-nonyl, decyl, undecyl, dodecyl radicals, or allyl, methallyl, 2-butenyl, 5-butenyl, J-pentenyl, propinyl, etc. radicals, and also methoxymethyl, methoxyethyl , ethoxyethyl, ethylthioethyl, dimethoxyethyl , diethoxyethyl , diethylthioethyl , methoxy- stituted for example by halogen, OH, SH, NOg, CN or CNS .

The active substances defined by formula (i) are ureas, carbamates or thiocarbamates . They can be prepared by methods that are known and described in the literature. The procedure may consist, for example, in (a) causing phosgene to act on . an aniline, when - depending on the reaction conditions employed - a carbanilic acid halide or a corresponding iso-cyanate is formed which is then further reacted with a compound of the formula HYB. The compound of the formula HYB may be an amine or an alcohol or a thioalcohol. These latter compounds can likewise be (b) reacted with phosgene, and depending on their constitution, the resulting carbamic acid chloride, isocyanate or alkylchlorocarbonate can be reacted with an aniline. By both procedures, (a) and- (b) , compounds, are obtained which are suitable according to the present invention. r- The active substances of the formula (l) have biocidal.' properties . ■ They have, for example, an antimicrobial, especially antibacterial,: action, for example against gram-positive organisms, such as Staph, aureus and against acid-resistant bacteria, such as M .tuberculosis . They also have a fungicidal or fungistatic action, for example against human- and phyto-pathogenic fungi. Moreover, they have an anthelmintic effect and an insecticidal and antiparasitic effect and are therefore useful as anthelmintics, and insecticides, and antipa asitics. When used as an aqueous dispersion or as a solution in an organic solvent , they have an affinity for keratin fibers and protect these fibers from infestation by pests, especially cationic surface-active compounds, such as soaps and synthetic wetting, emulsifying or washing agents, they do not lose their biocidal action. The compounds do not have an objectionable intrinsic odor and are well tolerated at least by healthy skin. They produce no toxic side-effects in warm-blooded animals when employed in the concentrations that are usual for disinfecting purposes.

Due to these properties, the washing and cleaning agents of this invention have a very wide field of application. They can be used, for example, in the soap and cosmetics industries, or quite generally for body care and hygiene, as disinfecting and preserving agents for a great variety of technical and natural products, and especially as washing and cleaning agents having a disinfecting and sanitizing action in household and industry. They can be applied in many different ways. There may be mentioneduas' ppssible modes- :of .application, for example their use in soap solutions, foam baths, sprays, especially', foam sprays, solutions in organic solvents, etc. This application includes biocidal dressings which mainly serve anti-. bacterial and antimycotic purposes.

. Particular interest is due to the use of the washing and cleaning agents of this invention for antimicrobial and antimycotic dressings on textile and non-textile fiber materials at any stage of their processing, and flat structures, as for example foils.. Of greatest interest is the treatment of fiber materials because it has been found that the active substances of the formula (i) take on a wide variety of fibrous materials substantively from an aqueous bath. apart from mineral fibers, such as for example, asbestos -above all cellulosic fibers, such as flax, sisal, coconut, raffia, and especially cotton, and nitrogenous fibers, such as leather and wool. Suitable synthetic fibrous materials include polyc nd.ensa>tes, as well;as■ polyadducts^and poly- -merisates, that is to say, -polymers in a broad sence, as also glass fibers. The polymer fibers may be derived from natural or synthetic polymers. Fibers of natural polymers are for example regenerated cellulose, and cellulose di- to triacetate Prom synthetic polymers are derived, for example, the polyester, polyamide, polyurethane , polyacrylonitrile , polyvinyl chloride and polyethylene fibers. Accordingly, these fiber materials can be given a permanent biocidal, preferably antibacterial and antimycotic dressing to protect them from in-festation by microorganisms and other pests by simply washing them with the washing and cleaning agents of this invention. Fibrous, materials finished in this manner are not only pro-tected themselves from infestation by microorganisms and fungi they also protect their direct Environment and thus prevent the occurrence of disagreeable body and perspiration odor which is likewise caused by microorganisms, this being of particular advantage in the case of fully synthetic and cellulosic fibrous textile material. The dressing so produced has a good resistance to chlorine and perborate.

The washing and cleaning agents of this invention contain in addition to the active compound of the formula (i) suitable solid or liquid additives. Such additives are, for example, the usual washing assistants and detergent substan especially alkali metal salts of high molecular fatty acids, or soap-free , detergent . substances as for example the anionic alkylarylsufonates, tetrapropylbenzene sulfonates, fatty alcohol sulfonates, condensation products from fatty- acids and methyl taurine, condensation products from fatty acid and. hydroxyethane sulfonic acid salts, fatty acid-protein condensation products, primary alkyl sulfonates, non-ionic products, for example condensation products from alkyl phenols and ethylene oxides, as well as cationic compounds. Washing assistants are here intended to mean compounds having little or no detergent power, but influencing the detergent properties of a washing agent. With them it is possible, for example, to adjust the pH of a washing liquor to an optimal value or to increase the dirt suspending capacity and the washing effect. Examples of such substances are for example electrolytes, such as for example trisodium phosphate, sodium diphosphate, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium meta.sili. cate or water-glass, cellulose glycollate, organic complex formers (dehardeners) , bleaches, optical brigh'teners, light-screening agents, antioxidants, perfumes, etc. The agents of this invention may also contain other biocidal substances, preferably fungicides and microbicides . Examples of such substances are, inter alia, 5, -dichlorobenzyl alcohol, ammonium compounds, as, for example, diisobutylphenoxyethoxy-ethyl-dime hyl-benzylammonium chloride, cetylpyridinium chloride, cetyl-trimethylammonium bromide, halogenated dioxydi-phenylmethane , tetramethylthiuram disulfide, 2,2-thio-bis-( ,6-dichlorophenol ) , also organic compounds which contain the dichlorocyanuric acid,, tetrachlorosalicylic anilide, aliphatic thiuram sulfides, hexachlorophene (2,2 '-dihydroxy-}^^-}1 , 5 ' ,6 T-hexachlorodiphenylmethane ) ; amphoteric disinfectants, such as dodecyl-di (aminoethyl) -glycine hydrochloride; further products are 5,6-dichlorobenzoxazolinone-(2) , 2 , ,4 ' -trichloro-2-hydroxy-diphenylether , iodophoric halogenphenols , 2-(furanyl) benzimidazole , 2- (thiazolyl ) -benzimidazole , trichlorocarbani-lide . Depending on the intended use, the agents of this invention may be present in various forms, for example, cake soaps, semi-liquid, and liquid soaps, as pastes, powders, emulsions, suspensions, solutions in organic solvents, as sprays, fine i powders, granules, tablets, in capsules made of gelatine or other material, or as salves.

The quantities in which the active compounds of the formula (i) are used may vary within wide limits. However, as a rule, 1 to }0 g per liter of liquor produce the desired effect. The washing and cleaning agents as a rule have a content of active compound of .0.5 to 10 per cent by weight, pre-ferably 0.5 to 3 per cent by weight.

As aforesaid, those compounds of the formula (I) in the agents of this invention in which the substituents and R^ each represents an F^C group, stands for hydrogen, and B for a branched alkyl radical with 5 to 10 carbon atoms have especially favorable properties. They are preferably ureas, that is to say, compounds in which Y represents the -NH- I group. Similarly good properties characterize those ureas in which B also represents a branched alkyl radical having 5 to 10 carbon atoms, but R^ stands for hydrogen, R^ for chlorine Example 1 37.6 parts of 3,4-dichlorophenyl isocyanate are added .to a solution of 25.'9 parts of 2-ethylhexyl-(l) -amine in 200 part, by volume of benzene. By the addition of 200 parts by volume of petroleum ether N-5,4-dichlorophenyl-N ' -2-ethylhexyl- (l ) - urea of the formula precipitates. The yield is about 7 parts (= compound l).

Melting' point : 65-66°C In an analogous manner to that described above the following ureas of the formula Ar - NH - CO - NH - B are obtained.

Example 2 When 1 mol of 3,^-dichlorophenyl isocyanate is heated with 1 mol of isopropyl mercaptan in benzene and in the presence of triethylamine , the compound of the formula is obtained which melts at 92. C. (Compound No. 51).

In an analogous manner the following compounds of the formula Ar - NH - C - O - B 0 may be obtained.

Example 3 The ureas and urethanes of formula (I) show an extremely strong activity against gram-positive bacteria, particularly against Staphylococci and Streptococci. They are also effective against pathogenic fungi such, for example, as Trichophyton interdigitale .

The antibacterial activity in the dilution test was determined as follows: Bacteriosta sis and bactericidal activity a) 20 mg of active substance are dissolved in 10 ml of propyleneglycol of which 0.25 ml is added to 4.75 ml of sterile Staphylococcus aureus and incubated for 48 hours at 57°C (bacteriostasis). After a test-time of 24 hours a loop from these cultures is spread on glucose agar plates and incubated for 2 hours at 57°C (bactericidal activity). After the times mentioned, the following limiting concentrations in ppm of bacteriostasis or bactericidal activity were found: Limiting concentrations in ppm Compound Staph . aureus Esch. coli -static/-cidal effect effect 1 0.5 9 1 / 5 100 / 100 0.5 / 0.5 100 / 100 12 0.5 / 0.5 100 / 100 / 5 100 / 100 1 / 1 100 / 100 22 5 / 5 100 / 100 0.05 / 0.01 . 1 / 1 40 0.1 0.5 54 0.5 / 0.5 59 0.5 / 0.5 68 5 / 5 100 / 100 Determination of the minimum inhibiting concentration (MIC) against bacteria and fungi in the gradient plate test The compounds of formula (i) are mixed in a suitable formulation (for example as a solution in dimethylsulphoxide ) of a certain concentration with warm brain heart infusion The cultures of Staphylococcus aureus are then applied linearly with a pasteur : pipette vertically to the gradient. After an incubation of 24 hours at °C the length of the germs that have grown on the inoculation line is measured and expressed in ppm of active substance.

Example 4 Pieces of 100 g of cotton-cretonne are impregnated with an 0.1 solution of N-3,4-dichlorophenyl-N ' -2-ethylhexyl- (l ) -urea in isopropanol at 20°C on a pad and then squeezed until-100$ of their weight of liquor are taken up.

Pieces of 100 g of cheviot wool are treated in the same manner .

The fabric dried at 50 to 40°C contains 0.1$ of active substance calculated on its own weight.

In order to test the effect against bacteria, disks (measuring 100 mm in diameter) of the impregnated fabric -unwatered, and after 24 hours watered at 29°C - are placed on glucose agar plates that have been previously inoculated with Staphylococcus aureus. The plates are then incubated for 24 hours at 37°C . .microscopically are. determined: Example 5 For the preparation of an antibacterial cake of soap the following mixture is added to 1.2 g of N-5,4-dichloro-phenyl-N ' -2-ethylhexyl- (l) -urea : 120 g of soap base in the form of flakes 0.12 g of the disodium salt of ethylenediamine tetraacetic acid (dihydrate) 0.24 g of titanium dioxide The soap chips obtained by .rolling are pulverized with a rapid stirrer and then compressed into cakes of soap. 2.5 g of the antibacterial soap are dissolved in 50 ml of tap water and glucose broth added to a quantity of 1 ml to ml of solution and to 1.5 to 5-5 ml of the solution, respectivel .' By continuous dilution to ten times the quantity in each case two series are obtained which result in the following continuous dilution series by being combined: 100, 50, 10, 5, 1, 0.5, 0.1 etc ppm of active substance. The separate solutions are inoculated with cultures of Staphylo coccus aureus and incubated for 24 hours at 57°C. After this are incubated for a further 24 hours at 37°C. The minimum inhibition or lethal concentration in the solutions and plates respectively, is determined: Activity against Staphylococcus aureus Bacteriostasis (48 hours) 1 ppm Bactericidal activity (24 hours) 1 ppm With aqueous preparations of these antibacterial soaps textile materials may, for example, be given an antibacterial dressing . hen washed because the active substance is absorbed substantively on. the textile material.

Example 6 Washing Test Sterile disks of cotton (j.O g) of 4 cm in diameter are each inoculated with 0.1 ml of a suspension of Staphylococcus aureus that contains 50 of sterile ox serum and 10^ germs, . and dried for 1 hour~at 37°C . The material is then washed in a laboratory washing apparatus using a goods-to-liquor ratio of 1 : 20 with 4 g per litre of a detergent built up on the basis of dodecylbenzene sulphonate , which contains 1 % of the active substance No. 25 or 42, for 15 minutes in the same goods-to-liquor ratio at 45°C, and three times for minutes each time at 20°C . The disks of fabric are then dried between sterile filter paper.

The lasting effect is determined as follows: The disks are placed on agar plates which have been previously inoculated with cultures of Staphylococcus aureus l8 hours old. These plates are then incubated for 24 hours Result : The disks treated with active substance No. 23 or 42 contain no colonies of Staphylococcus aureus and form a zone free from bacteria on the agar.

If the washing is carried out in the above Example at 95°C instead of at 45°C, similar results are obtained, active substance being optionally replaced by active substances Nosr.. 1, 24, 40, 41 or 50.

The curative effect (45°C washing temperature) is determined as follows: 4 disks treated with one of the active substances Nos. 1, 20, 23, 38, 40 to 46, 48 or 49 are each placed on an agar plate (brain heart infusion agar + 0.1$ yeast per litre of agar) and incubated at 37°C · After one hour the disks are removed from two of the plates and all 4 dishes incubated for a further 24 hours at 37°C.

The two agar plates where the disks were left for one hour are called dabbing plates and those on which the disks were left for 24 hours are called lasting contact plates.

Result: Neither on the two dabbing plates nor on the lasting contact plates are there any colonies of Staphylococcus aureus.

If instead of cotton disks, disks of nylon are used, similar curative effects are obtained.

Germ count of the washing water: 0.1 ml of the washing water (washing at 45°C) is applied to sterile agar plates (brain heart infusion agar + 0.1$ of east er litre of a ar . After an incubation time of 24 hours of the detergent which contains 1% of the active substances No. 1, 20, 25, 58, 40 to; 42, 48 or 49.

Claims (2)

1. V WHAT WE CLAIM IS: 1. Washing and cleaning agents containing as active component at least one carbanilic acid derivative of the general formula in which R^ represents hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN, Ν0≥ or CF^, R≥ stands for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN or O^, R^ for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN,. NO^ or CF^, and B for a branched, saturated or unsaturated aliphatic radical or a linear, unsaturated aliphatic radical containing 5 to 12 carbon atoms which may be interrupted by one or several oxygen and/or sulfur atoms, or stands for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN, NO^ or CF^, for hydrogen, bromine, lower alkyl, lower alkoxy, acyl, CN or NOg, R-j for hydrogen, halogen, lower alkyl, lower alkoxy, acyl, CN, O^ or CF^ and B for a linear, saturated or unsaturated aliphatic radical containing J to 12 carbon atoms which may be interrupted by one or several oxygen and/or sulfur atoms, at least one of the substituents R^, R≥ and R^ being different from hydrogen, and Y stands for an oxygen or sulfur atom or the NH group.

2. Washing and cleaning agents according to claim 1, which contain one or more of the., following liquid or solid additives: washing assistants, detergent substances, and further biocidal claims 1 and 2 , wherein each of the substituents R^ and represents a CF group, R2 stands for hydrogen, Y for NH, and B for a branched alkyl radical with 5 to 10 carbon atoms . Washing and cleaning agents according to claim ^containing as active substance the compound of the formula 5. Washing and cleaning agents according to claim 3 , containing as active substance the compound of the formula 6. Washing and cleaning agents according to either of claims - 1 and 2 , wherein represents hydrogen, R^ stands for chlorine or bromine, R' for chlorine, Y for NH, and B for a branched alkyl radical with 5 to 10 carbon atoms. 7 . Washing and cleaning agents according to claim 6 , containing as active substance the compound of the formula 8 . Washing and cleaning agents according to claim 6 , containing as active substance the compound of the formula 9. Washing and cleaning agents according to claim 6, containing as active substance the compound of the formula 10. Washing and cleaning agents according to claim 6, containing as active substance the compound of the formula 11. The use of the washing and cleaning agents defined in any one of claims 1 to 10 for producing biocidal dressings on textile or non-textile fibrous material or flat structures. 12. The use according to claim 11 for producing antibacterial or antimycotic dressings on textile or non-textile fibrous materials or flat structures. 15. The use according to claim 12 for producing antibacterial dressings on fully synthetic or cellulosic textile material .