DE2349293A1 - Cleansers and detergents with disinfectant activity - contg. anion-active 2-hydroxy-4-thia- or 2-hydroxy-4-aza-alkane sulphonates and cation- active surfactants - Google Patents

Abstract

Cleansing agent and detergent compsns. having disinfectant props. contain an anion-active surfactant consisting of >=1 cpd. having formula: R-CHY-CH2-X-CH2-CH(OH)-CH2-SO3M (I) (where R is 6-14C, esp. linear, alkyl or alkanoyl; X is NR1, R1N right arrow O, S or SO, R1 is H, Me, Et, (C2H4O)n-H or (CH2CHMeO)n-H; Y is H or OH; n is 1-4; M is valency of an alkali- or alkaline earth metal, NH4 or an organic ammonium base, but pref. Na) and a cation-active surfactant (II) consisting of a surface-active NH4 cpd. Wt. ratio (I):(II) is 20:1-3:1 (10:1-4:1). Compsns. are used for disinfectant wash of textiles, sanitary installations, medical instruments, hair- and skin-shampoos. Addn. of (I) improves bactericidal activity of compsn.

Description

Düsseldorf, September 2, 2018 1973: -. . . Hang! & Cie GmbH

Henkelstrasse 67 · "'' ί ^:> I ''

Patent application D 4805

Laundry detergents containing anion-active and cation-active surfactants

Mixtures of capillary-active anionic and cationic compounds are known from German patent applications B 23835 and DAS 1 264 663, which are suitable for use in disinfecting detergents and cleaning agents and cosmetic preparations. The anion-active compounds mentioned are those which, in addition to a sulfur or phosphoric acid ester group, contain a nonionic polyglycol ether group or two anionic groups. These include the salts of sulfosuccinic that ⁰ ^ -SuIf of ettsäuren and salts of unspecified characterized compounds containing two carboxyl groups in the molecule. When using these anionic surfactants, the undesired formation of poorly soluble electron neutral salts is prevented and the disinfecting effect of the cationic surfactants is supposed to be partially retained. However, there is no experimental confirmation of this claimed advantage and a follow-up test shows that the disinfecting effect of the mixtures is not yet satisfactory. The present invention provides a substantial improvement in this regard.

The invention relates to detergents and cleaning agents containing anionic and cationic surfactants with improved disinfectant effect, which is characterized are that the anion-active surfactant consists of at least one compound of the following formula

R - CHY - CH ₂ - X - CH ₂ - CH (OH) - CH ₂ - SO ₃ Me

wherein R is an alkyl or alkenyl radical having 6 to 14 carbon atoms, X the groups NR ', R'-N ^ O, S or SO, R' the groups H,

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CH _3,. C ₂ H ₅ , (CH ₂ CH ₂ O) _n -H or [CH ₂ CH (CH ₃ ) Oj _n -H, I the groups H or OH, η a number from 1 to 4 and Me the valence of an alkali or alkaline earth metal of ammonium or an organic ammonium base mean that the cation-active surfactant consists of a capillary-active ammonium prebond and the weight ratio of anion-active to cation-active compound is 20: 1 to 3: 1.

Suitable compounds of this class are, for example: 2-Hydroxy-4-thiaalkanesulfonic acid salts of the formulas R-CH ₂ -CH ₂ -S-CH ₂ -CH (OH) -CH ₂ SO ₃ Me (I)

R-CH (OH) -CH ₂ -S-CH ₂ -CH (OH) -CH ₂ SO ₃ Me (II)

R-CH ₂ -CH ₂ -S-CH ₂ -CH (OH) -CH ₂ SO ₃ Me (in)

wherein R is an alkyl or alkene radical having 6 to 14 carbon atoms stands and Me has the aforementioned meaning; further

2-Hydroxy-4-aza-alkanesulfonic acid salts of the formulas R-NH-CH ₂ -CH (OH) -CH ₂ SO ₃ Me (IV)

RN-CH ₂ -CH (OH) -CH ₂ SO ₃ Me (V)

RN-CH ₂ -CH (OH) -CH ₂ SO ₃ Me (VI)

CH ₂ CH ₂ OH

0
R - ^ - CH ₂ -CH (OH) -CH ₂ SO ₃ Me (VII)

CH ₂ CH ₂ OH

wherein R is an alkyl radical having 8 to 16 carbon atoms and Me has the aforementioned meaning.

Preferably, R is a straight-chain alkyl radical, e.g. B. a hexyl, octyl, decyl, dodecyl, tetradecyl or hexadecyl radical and their mixtures, such as those from

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natural fats, e.g. coconut or palm kernel fats the uxosynthesis or from petroleum hydrocarbons or are obtainable by 'ethylenpolymerisation. Me can e.g. Na, K, mono-, di- or triethanolamine, morpholine or Be N-methylmorpholine. The sodium salts are preferred used. .

The compounds can be prepared in a known manner by reacting amines or mercaptans of the formula R-CHY-CH ₉ -NHR ¹ or R-CHY-CH ₉ -SH with S-chloro-α-hydroxypropanesulfonate-1 and, if appropriate, subsequent oxidation the corresponding amine oxides and sulfoxides take place.

Suitable cationic ammonium compounds are those which contain an aliphatic hydrocarbon radical with at least 10 to at most 20 carbon atoms and 3 aliphatic or aromatic radicals or a das Contain heterocyclic radical containing quaternary nitrogen atoms, these radicals no longer in each case should have than 8 carbon atoms. The cation-active Surfactants should be soluble in water,

Suitable are, for example, stearyl-dimethyl-benzylammonium chloride, cetyl-trimethyl-ammonium chloride, myristyl-diethyl-benzylammonium chloride, lauryl-tri-ethyl-ammonium chloride, oleyldimethyl-hydroxyethylammonium chloride, stearyl-dimethyl-hydroxyethylammonium chloride, analogous compounds of cetylpyridinium chloride, cetylpyridinium chloride, laurylpyridinium-pyridinium chloride , in which the C ₁ QC ₂₀ -alkyl radicals represent mixtures with different chain lengths. Instead of the chloride anion, bromide, sulfate, methosulfate, ethosulfate, acetate, lactate or any other anions can be present *

Preferably the weight ratio is more anion active too cationic - r substance 10: 1 to 4: 1.

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In addition to the mixtures according to the invention, the detergents preferably contain at least one builder substance as well as other common ingredients in detergents and cleaning agents.

Suitable builder substances are the polymer phosphates, carbonates and silicates of potassium and, in particular, of sodium, the latter having a ratio of SiOp to Na ₂ O of 1: 1 to 3.5 i 1. Particularly suitable as the polymer phosphate is pentanatriuratriphosphate, which can be present in a mixture with its hydrolysis products, the mono- and diphosphates, and more highly condensed phosphates, for example the tetraphosphates. ■

The polymer phosphates can also be completely or partially replaced by organic, coraplexing aminopolycarboxylic acids. These include in particular alkali salts of nitrilotriacetic acid and ethylenedianiinotetraacetic acid. The salts of diethylenetriarainopentaacetic acid and the higher homologues of the aminopolycarboxylic acids mentioned are also suitable. These homologues can be produced, for example, by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acid salts or by reacting polyethyleneimine with chloroacetic acid or bronze acetic acid salts in an alkaline medium. Other suitable aminopolycarboxylic acids are poly (N-succinic acid) ethyleneimine, poly (N-tricarballyic acid) ethyleneimine and poly (W-butane-2, 3 , 4-tricarboxylic acid) ethyleneimine, which are obtainable analogously to the K-acetic acid derivatives

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In addition, complexing polyphosphoric acid can be used Salts be present, e.g. ' the alkali salts of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), 1-hydroxyl * than-1,1-dipho-sphonic acid, Ksthylenediphosphonic acid, Ethylenediphosphonic acid and salts of the higher Homologues of the polyphosphonic acids mentioned. Mixtures too the aforementioned complexing agents can be used,

Of particular importance are the nitrogen- and phosphorus-free polycarboxylic acids that form complex salts with calcium ions, including polymers containing carboxyl groups. Citric acid, V / one acid, benzene hexacarboxylic acid are suitable and tetrahydrofuran tetracarboxylic acid. Polycarboxylic acids containing carboxymethyl ether groups are also used useful, such as 2,2 '~ oxydisuccinic acid as well as with glycolic acid partially or completely etherified polyhydric alcohols or hydroxycarboxylic acids, for example trisearboxyraethylglycerol, Biscarboxymethylglyceric acid and carboxymethylated bzv /. oxidized polysaccharides, are also suitable the polymeric carboxylic acids with a molecular weight of at least 350 in the form of the water-soluble sodium or Potassium salts, v / ie polyacrylic acid, polymethacrylic acid, polycc-hydroxyacrylic acid, Polymaleic acid, polyacetic acid, polymesaconic acid, polybutenetricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, Propylene, isobutylene, vinyl methyl ether or furan.

Complexing agents which are insoluble in water can also be used. These include phosphorylit cellulose and graft polymers acrylic acid or methacrylic acid on cellulose, which can be in the form of fabrics, nonwovens or powders. Furthermore, they are spatially cross-linked and therefore insoluble in water

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made copolymers of acrylic, methacrylic, croton and Maleic acid and other polymerizable polycarboxylic acids, optionally with further .äthylenisch unsaturated compounds in the form of sodium or potassium salts as sequestrants suitable. These insoluble copolymers can be used as fleeces, sponges or in the form of finely ground, specifically lighter foams with an open-cell structure are present.

Oxygen-releasing bleaching agents, such as alkali metal perborates, alkali percarbonates, perpyrophosphates and persilicates, and urea perhydrate, may be used as a further constituent of the mixture. Sodium perborate tetrahydrate is preferably used. For the purpose of stabilization of peroxy compounds, the compositions may contain magnesium silicate, "for example, in amounts of from 3 to 20 wt .- ^ _1. The amount of perborate. To Textilv / mullet applied at temperatures below 70-C agent, so-called ICaltwaschmittel bleach activators, in particular tetraacetylglycoluril or tetraacetylethylondiarain as powder constituent. The powder particles consisting of the bleach activator or the per compound can be coated with coating substances, such as water-soluble polymers or fatty acids, in order to avoid a bad effect between the per compound and the activator during storage.

The agents can also contain enzymes from the class of proteases, lipases and amylases or mixtures thereof. Particularly suitable idnd from bacterial strains or fungi, v / ie Bacillus enzymatic agents obtained from subtilis, Bacillus licheniformis and Streptoiayces griseus.

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Particularly suitable graying inhibitors are carboxymethyl cellulose, Methyl cellulose, furthermore water-soluble polyesters and polyamides made from multicarboxylic acids and Glycols or diamines, which enabled free salt formation Have carboxyl groups, betaine groups or sulfobetaine groups as well as polymers or copolymers which are colloidally soluble in water of vinyl alcohol, vinyl pyrrolidone, acrylamides and acrylonitrile.

Other ingredients include neutral salts, in particular Sodium sulfate. Liquid agents can also contain hydrotopic substances and solvents, such as alkali salts benzene, toluene or xylene sulfonic acid, urea, Glycerine, polyglycerine, di- or triglycol, polyethylene glycol, Ethanol, i-propanol and ether alcohols.

The detergents can optionally also contain known foam suppressants, such as saturated fatty acids or their alkali metal soaps with 20 to 2k carbon atoms, higher molecular weight fatty acid esters or triglycerides, paraffins, trialkylmelamines. and silicone antifoams. '

The detergents can also contain optical brighteners, in particular derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable are e.g. ' Salts of the 4,4 "-bis ("2" -anilino-A "" i! Iorpholino-1,5,5-triasinyl-6 "-amino) -stilbene-2,2'-dlsulfonic acid or similarly structured compounds which instead of the morpholino group are a diethanolamino group, a methylanino group or a ß-methoxyäthylaiaii: · ο group carry. Other possible brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1 - <- p-sulfonaiüidophenyl) -3- (p-chlorophenyl) - ^ "- pyrcsolin and similarly structured compounds that instead of the sulfonaraidogruppo a Garboxyraethyl- or Acet.ylaminof, ruppc wear. Substituted aminocuniarilles, κ, B are also useful. the A-methyl-T-diraethylamino or the

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Α-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidalolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can also be used as polyainide brighteners. The compounds 2,5-di- (2-ben2oxazolyl) -thiophene, 2 ~ (2 ~ benzoxazolyl) -naphtho \ jL, 3- ^ b] -thiophene and 1,2-di- are used as brighteners for polyester and polyamide fibers. (5ririethyl-2-benzoxa2olyl) -ethylene suitable. Furthermore, brighteners of the substituted diphenyl-styrenic type can be present. Mixtures of the abovementioned brighteners can also be used.

If necessary, additional compounds with cationic activity can be used Compatible surfactants may be present, for example nonionic polyglycol ether derivatives of alcohols, fatty acids and alkylphenols containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon residue. Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 are particularly suitable and their hydrocarbon radicals are derived from straight-chain, primary alcohols having 12 to 18 carbon atoms or from alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms. Further suitable Nonionic detergent raw materials are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Containing polyethylene oxide adducts with polypropylene glycol and ethylene diamine polypropylene glycol. the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

The agents according to the invention have good cleaning and bactericidal properties and show no precipitations in aqueous solution. They are ideal for disinfecting cleaning of textiles, sanitary facilities, medical equipment sov / ie for skin and hair washing.

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Examples Example 1 to 6

As the anion-active compounds, they have become as follows Formula used:

R - CHT - CH ₂ - X - CH ₂ - CH (OH) -

Abbreviation R-CHY-CH ₂ - X S. ^A 1 ^C 8 ^H 1J S. A ₂ C ₈ H ₁₇ -CHOH-CH ₂ S = O A, C ₁₂ H ₂₅ 'NH - v C ₁₂ H ₂₅ N-CH ₂ CH ₂ OH ^A 5 Coconut alkyl Q- ^ N-CH ₂ CH ₂ OH ^A 6 Coconut alkyl

The coconut alkyl radicals consist essentially of C ₁₂ alkyl radicals with a smaller proportion of CUq or alkyl radicals.

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The following were used as catalyst surfactants:

C.j 2 ~ C-i g-Alkyl-dimethylaniTnonlurttchlorid. (K.), Lauryl pyridinium chloride (Kp) ■ ♦

Aqueous solutions containing 2 g / l of the aforementioned anion and cation surfactants in varying composition containing, were incubated at 20 ⁰ C with a seed suspension of E. coli and Staph. aureus is added (0.2 ml suspension to 10 ml test solution). After 5 minutes, samples were taken and streaked onto agar culture media containing additives to eliminate development inhibition. After a 3ebrütungszeit 48 hours at 37 ⁰ C the bacterial count was determined. The following table shows the percentage of cationic surfactants in the total amount of surfactant present, which is sufficient to kill all germs within 5 minutes. A low percentage is synonymous with a high bactericidal effect. For comparison, the disodium salt of coconut alcohol sulfosuccinic acid half-ester (alkyl radical C - ^ - ^ IS ¹ middle chain length C ^, designation A ¹ ) and the disodium salt of an oC sulfo fatty acid, produced from hydrogenated palm kernel fatty acid (designation A ") are included in the experiments. The results show that the agents according to the invention are more effective than the known mixtures.

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example Anionic surfactant Cationic surfactant Child share
Cationic surfactant for
Killed in 5 min.
(into the") 1 ^A 1 ■ * 1. 20th CVl A ₂ K ₁ 10. 3 ^A 3 K ₁ 10 4th V ' K ₁ 15th 5 ^A 5 ^K 1 10, 6th ^A 6 ^K 1 10 7th ^A 1 . K ₂ 20th 8th A ₂ K ₂ 10, 9 A ₃ K ₂ 10 10 ^A 4 K ₂ 20th 11 ^A 5 K _2:. 10. 12th ^A 6 K ₂ 10 - A ^{1 K} 1 45 - A ¹ K ₂ 40 - A " K ₁ ■ 30th A " K ₂ 30th

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Example 15

A detergent with the following composition was produced (in percent by weight)

20 % anionic surfactant A ^ (according to example 4)

2 % iauryl pyridinium chloride
30 % pentasodium tripolyphosphate 18? Ί sodium sulfate

5 % sodium silicate (Na ₂ OiSiO ₂ = 1 i 3.3) 2-6 Na-ethylenediaminetetraacetate 15% sodium perborate
1.5% sodium carboxymethyl cellulose 0.3. % optical brighteners

The detergent was used in a concentration of 7.5 g / l. According to an experiment conducted at 60 ⁰ C washing test (washing time 20 minutes bath ratio 1: 12) was found to wash the treated as a germ-free.

Example 14

A composition shampoo

30 % anionic surfactant A ₆ (according to Example 6) 3 % cationic surfactant K ^

5 % fatty acid diethanolamide
Rest water

showed good germicidal properties and proved to be extremely skin-friendly.

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Claims (5)

Henkel & Cie GmbH patent department patent claims 1. Washing detergents containing anionic and cationic surfactants and cleaning agents with improved disinfecting effect, characterized in that the anionic surfactant consists of at least one compound of the following formula R - CHY - CH ₂ - -X - CH ₂ - CH (OH) - CH ₂ - SO ₅ Me where R is an alkyl or alkene radical with 6 to 14 carbon atoms, X is the groups NR ¹ , R'-N-jO, S or SO, R ^{1 is} the groups H, CH ₅ , C ₂ H ₅ , (CH ₂ CH ₂ O ) _n -H or £ cH ₂ CH (CH ₃ ) O] _n -H, Y denotes the groups H or OH, η denotes a number from 1 to 4 and Me denotes the valence of an alkali or alkaline earth metal of ammonium or of an organic ammonium base, that further -the cation-active surfactant consists of a capillary-active ammonium compound and the weight ratio of anion-active to cation-active compound is 20: 1 to 3 s -1. 2. Composition according to claim 1, characterized in that the weight ratio of anion-active to cation-active Surfactant is 10: 1 to 4 x 1. 3. Means according to claim 1 and 2, characterized in that in the formula of the anion-active surfactant R, a straight-chain one Represents alkyl or alkene radical. 4. Means according to claim 1 to 3, characterized in that that in the formula of the anionic surfactant Me stands for sodium. 5. Means according to claim 1 to 4, characterized in that the cationic ammonium compound is an aliphatic hydrocarbon radical with 10 to 20 carbon atoms -14- 509815/1220 Henkel & Cie GmbH Patent department and 3 aliphatic or aromatic radicals or one nitrogen-containing heterocyclic radical each having not more than 8 carbon atoms. 6, - means according to claim 1 to 5, characterized by a Content of at least one structural substance from the class of polymer phosphates, carbonates, silicates, polycarboxylic acids and polyphosphonic acids in the form of the alkali salts. 509815/122 0