DE2349293C3 - Washing and cleaning agents containing anionic and cationic surfactants - Google Patents

Description

From the German patent applications B 23 835 and DE-AS 12 64 663 are mixtures of capillary-active anionic and cationic compounds known for use in disinfecting Washing and cleaning agents and cosmetic preparations are suitable. As anion-active compounds those are named which, in addition to a sulfur or phosphoric acid ester group, have a nonionic polyglycol ether group or contain two anionic groups. These include the salts of sulfosuccinic acid half esters, of a-sulfofatty acids and salts of not more closely characterized compounds with two carboxyl groups in the molecule. When using this anion-active surfactants, the undesired formation of poorly soluble electron neutral salts is prevented and the disinfecting effect of the cationic surfactants is said to be partially retained. One However, there is no experimental confirmation of this claimed advantage and verification shows that the disinfecting effect of the mixtures is not yet satisfactory. The present invention provides in a substantial improvement in this regard.

The invention relates to washing and cleaning agents containing anionic and cationic surfactants with improved disinfecting effect, which are characterized in 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

where R is an alkyl or alkenyl radical with 6 to 14 carbon atoms, X is the groups NR ', R'-N - * O, S or SO, R' is the groups H, CH ₃ , 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, π 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 the cation-active surfactant also consists of a capillary-active ammonium compound and the weight ratio of anion-active to cation-active compound is 20: 1 to 3: 1.

Suitable compounds of this class are e.g. E.g .: 2-hydroxy-4-thiaalkanesulfonic acid salts of the formulas

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

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

(H)

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

Il 0 °)

in which R is an alkyl or alkene radical having 6 to 14 carbon atoms 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)

50

55

60 RN-CH ₂ -CH (OH) -CH ₂ SO ₃ Me

CH ₃

(V)

RN-CH ₂ -CH (OH) -CH ₂ SO ₃ Me CH ₂ CH ₂ OH (VI)

RN-CH ₂ -CH (OH) -CH ₂ SO ₃ Me

CH ₂ CH ₂ OH

(VII)

where R stands for 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 mixtures thereof, such as those from natural fats, ζ. B. coconut or if palm kernel fats, from the oxo synthesis or from petroleum

j hydrocarbons or ethylene polymerization

I are available. Me can e.g. B. Na, K, mono-, di- or Λ triethanolamine, morpholine or N-methylmorpholine ■ be. The sodium salts are preferably used

I- The preparation of the compounds can be carried out in a known manner

U way by reacting amines or mercapta

fi ning formula R-CHY-CH ₂ -NHR 'or R-CHY-

i | CH ₂ -SH with S-chloro-S-hydroxypropanesulfonate-l and

Ü, if necessary, subsequent oxidation to

\ £ speaking amine oxides and sulfoxides.

t |. As cationic ammonium compounds come

iä. consider those that have an aliphatic hydrocarbon

II hydrogen residues with a minimum of 10 to a maximum of 20 i | Carbon atoms and 3 aliphatic or aromatic

I radicals or one containing the quaternary nitrogen atom

| j tend to contain heterocyclic radicals, these

| j radicals in each case not more than 8 carbon atoms

; should have. The cationic surfactants should be used in

j j; Be soluble in water.

I; Suitable are e.g. B.

t ^! Stearyl-dimethyl-benzylammonium chloride,

jT? Cetyl trimethyl ammonium chloride,

f: Myristyl-diethyl-benzylammonium chloride,

S lauryl trimethyl ammonium chloride,

^:: Oleyldimethyl-hydroxväthylammoniumchlorid,

|: Stearyl-dimethyl-hyd. ^ ethylammonium chloride,

V laurylpyridinium chloride,

Cetyl pyridinium chloride

1 and analog connections in which the

! C10-C ₂ O-alkyl radicals mixtures with different

! Represent chain length. Instead of the chloride anion

₀ , bromide, sulfate, metbosulfate, ethosulfate,

Acetate, lactate or any other anions are present.

The weight ratio of anion-active to cation-active substance is preferably 10: 1 to 4: 1.

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 SiO ₂ to Na ₂ O of 1: 1 to 3.5: 1. Particularly suitable polymer phosphate is pentasodium triphosphate, which in a mixture with its hydrolysis products, the mono- and diphosphates and more highly condensed phosphates, ζ. B. the tetraphosphates, may be present.

The polymer phosphates can also be wholly or partly by organic complexing agents Aminopolycarboxylic acids replaced. These include in particular alkali salts of nitrilotriacetic acid and Ethylenediaminetetraacetic acid. The salts of diethylenetriaminopentaacetic acid and e> o are also suitable the higher homologues of the aminopolycarboxylic acids mentioned. These homologues can, for example by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by converting f> 5 Polyethyleneimine can be produced with chloroacetic acid or bromoacetic acid salts in an alkaline medium. Further suitable aminopolycarboxylic acids are

Poly (N-succinic acid) ethyleneimine,
Poly (N-tricarballyic acid) ethylene imine and
Poly (N-butane-2,3,4-tricarboxylic acid) ethyleneimine,
which are available analogously to the N-acetic acid derivatives.

Furthermore, complexing polyphosphonic acid salts can be present, for. B. the alkali salts of aminopolyphosphonic acids, in particular
Aminotri (methylenephosphonic acid),
1-hydroxyethane-1,1-diphosphonic acid,
Methylenediphosphonic acid,
Ethylene diphosphonic acid

and salts of the higher homologues of the polyphosphonic acids mentioned. Also mixtures of the aforementioned Complexing agents can be used.

Of particular importance are the nitrogen and phosphorus-free salts that form complex salts with calcium ions Polycarboxylic acids, including polymers containing carboxyl groups. Are suitable Citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid. Also carboxymethyl ether groups containing polycarboxylic acids are useful such as 2,2'-oxydisuccinic acid as well as with glycolic acid partially or completely etherified polyhydric alcohols or hydroxycarboxylic acids, for example Triscarboxymethylglycerin, biscarboxymethylglyceric acid and carboxymethylated or oxidized polysaccharides. The polymeric carboxylic acids with a molecular weight of at least are also suitable 350 in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, Poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, Polymesaconic acid, polybutenetricarboxylic acid and the copolymers of the corresponding monomers 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 phosphorylated Cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which are used as fabrics, nonwovens or can be in the form of a powder. Furthermore, they are spatially cross-linked and thereby rendered water-insoluble Copolymers of acrylic, methacrylic, crotonic and maleic acids, as well as other polymerizable ones Polycarboxylic acids, optionally with other ethylenically unsaturated compounds in the form of sodium or Potassium salts suitable as sequestering agents. These insoluble copolymers can be used as fleeces, sponges or in the form of finely ground, specifically light foams with an open-cell structure.

Oxygen-releasing bleaches such as alkali perborates, -percarbonates, -perpyrophosphates and -persilicates as well as urea perhydrate in question. Is preferred Sodium perborate tetrahydrate is used. In order to stabilize the per compounds, the means Magnesium silicate contain, for example in amounts of 3 to 20 wt .-%, based on the amount of Perborate. So-called cold detergents to be used for washing textiles at temperatures below 70 ° C Bleach activators, especially tetraacetylglycoluril or tetraacetylethylenediamine, can be used as a powder component contain. The powder particles consisting of the bleach activator or the per compound Knowing about coating substances such as water-soluble polymers or fatty acids coated to allow interaction between the per compound and the Avoid activator during storage.

The agents can also include enzymes from the class of proteases, lipases and amylases or mixtures thereof contain. A-is bacterial strains are particularly suitable or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.

Particularly suitable graying inhibitors are carboxymethyl cellulose, methyl cellulose, and also water-soluble ones Polyesters and polyamides made from polybasic carboxylic acids and glycols or diamines, the free have carboxyl groups, betaine groups or sulfobetaine groups capable of salt formation and Polymers or copolymers of vinyl alcohol, vinyl pyrrolidone, acrylamide and colloidally soluble in water Acrylonitrile.

Neutral salts, in particular sodium sulfate, can also be used as further constituents. Cash and cash equivalents can also contain hydrotopic substances and solvents, such as alkali salts of 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 24 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 diaminosulbendisulfonic acid or their alkali metal salts. Suitable are e.g. B. Salts of 4,4'-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyI-6 "-amino) -stilbene-2,2'-disulfonic acid or

similarly structured compounds which, instead of the morpholino group, carry a diethanolamino group, a methylamino group or a is-methoxyethylamino group. Also suitable as brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (- p-sulfonamidophenyl) -3- (pchlorphenyl) -4 ² -pyrazoline and similarly structured compounds which have a carboxymethyl or acetylamino group instead of the sulfonamido group. Substituted aminocoumarins, e.g. B. 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin. The compounds are also used as polyamide brighteners

1 - (2- Benzimidazolyl) -2- (1 -hydroxyethyl-

2-benzimidazolyl) ethylene and
l-ethyl-3-phenyl-7-diethylamino-

carbostyril

useful. As brighteners for polyester and polyamide fibers, the compounds are

2,5-di- (2-benzoxazolyl) thiophene,
2- (2-benzoxazolyl) naphtho-

[2,3-b] thiophene and

1,2-di (5-methyl-2-benzoxazolyl) ethylene
suitable. Furthermore, brighteners of the substituted diphenylstyrile type can be present. Mixtures of the abovementioned brighteners can also be used.

If necessary, other surfactants compatible with cationic compounds can also be present be, for example, nonionic polyglycol ether derivatives of alcohols, fatty acids and alkylphenols, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms inl hydrocarbon residue. Particularly suitable and polyglycol ether derivatives, in which the number of the ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals differ from straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols with a straight chain, 6 to Derive 14 carbon atoms containing alkyl chain. Other suitable nonionic washing 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 diamino 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 in aqueous solution no precipitations. They are ideal for disinfecting cleaning Textiles, sanitary facilities, medical equipment and for washing skin and hair.

Examples Examples 1 to 6

The following formula were used as anion-active compounds:

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

Short R-CHY-CH ₂ - X designate tion A ₁ CeH 17 S. A ₂ C ₈ Hi ₇ -CHOH-CH ₂ S. A, C) ₂ H ₂₃ S = O A ₄ C] ₂ H ₂₃ NH A ₅ Coconut alkyl N-CH ₂ CH ₂ OH A ₆ Coconut alkyl O <-N-CH, CH ₂ OH

The coconut alkyl radicals consist essentially of Ci 2 - Cn-alkyl radicals with a smaller proportion of Cio or C16 —Cie-alkyl radicals.

The following cationic surfactants were used: C12 - Cie-alkyl-dimethylammonium chloride (K.), laurylpyridinium chloride (K2).

Aqueous solutions containing 2 g / l of the aforementioned anion and cation surfactants in varying composition were contained at 2O 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 an incubation time of 48 hours the germ count was determined at 37 ° C. The table below 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 C12 - Qe, mean chain length Cu, designation A ') and the disodium salt of a «-sulfotatty acid, produced from hydrogenated palm kernel fatty acid (designation A") were included in the experiments. The results show that the agents according to the invention are more effective than the known mixtures.

example

Anion Surfactant Cation Surfactant

A ₁
A ₂
A ₁
A ₄
A,
A ₆

Aj

Ai
A,
A ₄
A ₅
A ₆

A '
A '
A "
A "

Minimum proportion of cationic surfactant to kill in 5 min.

(in %)

K ₁ 20

K ₁ 10

K ₁ 10

K, 15

K ₁ 10

K ι 10

K, 20

K ^ IO

K ₂ 10

K, 20

K, 10

K ₂ 10

K ₁ 45

K, 40

K, 30

K, 30

Example 13

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

20%

0.3%

Anion surfactant As (according to Example 4) Laurylpyridinium chloride Pentasodium tripolyphosphate Sodium sulfate Sodium silicate (Na ₂ O: SiO ₂ = 1: 3.3)

Na ethylenediaminetetraacetate sodium perborate sodium carboxymethyl cellulose 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 Liquor ratio 1:12), the treated wash proved germ-free.

Example A shampoo of the composition

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 kind to the skin.

Claims (6)

Patent claims: 1. Detergents and cleaning agents containing anionic and cationic surfactants with improved disinfecting effect, characterized in that the anion-active surfactant from consists of at least one compound of the following formula to R-CHY-CH ₂ -X-CH ₂ -CH (OH) -CH ₂ -SO ₃ Me wherein R is an alkyl or alkenyl radical with 6 to 14 carbon atoms, X the groups NR ', R'-N -O, S or SO, R' the groups, 5 H, CH ₃ , C ₂ H ₅ , (CH ₂ CH ₂ O) _n —H or [CH ₂ CH (CHCH ₃ ) O] _n —H, Y 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 of an organic ammonium base mean that the cation-active surfactant also consists of a capillary-active ammonium compound and the weight ratio of anion-active to cation-active compound is 20: 1 to 3: 1 2. Composition according to claim 1, characterized in that the weight ratio of anion-active to cationic surfactant is 10: 1 to 4: 1. 3. Composition according to claim 1 and 2, characterized in that the anion-active in the formula Surfactants R represents a straight-chain alkyl or alkene radical. 4. Composition according to claim 1 to 3, characterized in that the anion-active in the formula Tensides Me stands for sodium. 5. Composition according to claim 1 to 4, characterized in that the cationic ammonium compound an aliphatic hydrocarbon radical having 10 to 20 carbon atoms and 3 aliphatic or aromatic radicals or one nitrogen-containing heterocyclic radical each having no more than 8 carbon atoms. 6. Agent 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.