DE2153477C3 - Detergents and cleaning agents - Google Patents

Description

R '

-CH ₂ -N - (CH ₂ J _n SO ₃ R "

10

R "

where R is a straight or branched chain alkyl group having 8 to 24 carbon atoms, R 'and R "are each an alkyl group having 1 to 6 carbon atoms and π I to 4 , the weight ratio of the sulfobetaine to the nonionic surfactant being 9: 1 to 1 : 9 is

2. Washing and cleaning agent according to claim 1, characterized in that π means 3

3. Washing and cleaning agent according to claim 1 or 2, characterized in that R is a Denotes an alkyl group having 8 to 18 carbon atoms

4. Washing and cleaning agent according to one of claims 1 to 3, characterized in that R represents a straight chain alkyl group having 10 to 14 carbon atoms

5. Washing and cleaning agent according to one of claims 1 to 4, characterized in that R ' and R "are each methyl or ethyl groups.

6. Washing and cleaning agent according to one of claims 1 to 5, characterized in that the Sulfobetaine a 3- (N-linear-alkylbenzyl-N, N-dimethylammonio) -propane-1-sulfonate has an average of 12 carbon atoms in the alkyl group having

45

The present invention relates to a detergent containing a detergent nonionic surfactants based on polyethoxy compounds and a sulfobetaine, the is characterized in that the sulfobetaine is one of the general formula

R '

55

where R is a straight or branched chain alkyl group having 8 to 24 carbon atoms, R 'and R "are each an alkyl group having 1 to 6 carbon atoms and η is 1 to 4, the weight ratio of the sulfobetaine to the nonionic surfactant being 9: 1 to 1 : 9 is.

In BE-PS 7 56 880 are zwitterionic alkylbenlyl-di-lower alkylammonio-alkanesulfonates and these containing soap-based detergents described. It has now surprisingly been found that Mixtures of these zwitterionic detergents with nonionic polyide oxide detergents improved and Have unexpected cleaning properties.

From DT-AS12 57 338 low-foaming detergents and cleaning agents with a content of water-soluble melamine derivatives are known which _{can contain C 12 to} Cie-Alkyidimethylammonio-propanesulfonate and Fettaifcoholpolyglykoläther with a C _i2 - to Cj ₈ -alkyl group and 10 ethylene glycol groups the aforementioned fact is surprising to this document.

Usual synthetic detergents, especially the widely used anionic detergents or mixtures of anionic and nonionic detergents, when they are "fully built up" and used in hot water, clean cotton and even polyamide fabrics in an entirely satisfactory manner. They are "less unbuilt · sustainably," or they are at lower temperatures, for example below about 6O ⁰ C, used as gehl their cleaning power but rapidly lost, especially in connection with the removal of greasy dirt from polyamide fabrics. Even under the best of conditions, their ability to remove greasy soil from polyester or polyester-containing fabrics is poor. Furthermore, their ability to prevent soil redeposition is poor, particularly on cotton and polyester fabrics.

To explain the expressions »fully scaffold tig "and" less builder-containing "is indicated that an important function of a detergent Builder consists in the presence of the detergent and cleaning agent mixture and the soiled Wash water to bind the components of hard water in particular calcium ions, complex or ir Hold solution. Thus, in a washing process in which, together with a sufficient amount of ar organic surface-active agent there is sufficient grain plex-forming builder compound around all to bind existing calcium ions in a complex way, because! System referred to as “full of builders” If aul Due to improper composition or, what is not unusual, as a result of the use of a wash and detergent in a concentration lower than that for which the middle has been formulated that there is insufficient builder to achieve this result, the system will ah "Contains less builders"

It has surprisingly been found that the detergents and cleaning agents according to the invention also are excellent at cleaning natural fiber fabrics such as cotton products, even if they are contain less builder or a less strongly chelating builder than conventional detergents de detergents and cleaning agents. The! but means that with comparable detergency an eutrophication of waters through the wash liquor wastewater can be reduced considerably The agents according to the invention have persistently good cleaning and dirt suspension properties, ins special under the washing conditions and be those fabrics where the usual washing unc Detergents prove weak.

As has been demonstrated on the basis of comparative tests (cf. Examples 2 and 3), the Laundry detergents and cleaning agents according to the invention without reducing the washing power a reduction in the in

, Phost, which is undesirable for environmental protection, or a partial replacement of the phosphate, more environmentally friendly citrate, whereby even ver? ejse an increase in washing power occurs, special zwitterionic component, & h. that of the washing and cleaning title according to the invention can be produced in the manner described in BB-PS 7 56 880 j of the above general formula, R is preferably a straight-chain alkyl group having 8 to 18 carbon atoms, in particular 10 to 14 carbon atoms; ö R ″ are preferably ethyl or methyl, 'j methyl groups; α is preferably 2 or ', 3. Advantageously, this compound is a J ^ inear-alkylbenzyldimethylammonio) -pro-1-sulfonate, preferably 3- (dodecylbenzyldimeapan-1-sulfonate, i.e. it has 112 carbon atoms in the alkyl group. Nonionic component can Any nonionic polyethoxy detergent or one which contains a mixed polyethoxy / polypropoxy group. Preferred compounds are those based on alcohols or alkylphenols as the ubophilic part which have the general formula

R '"-0 [(CHz) ₂ O] _x H

wherein R '"is an alkyl group having 10 to 18 carbon atoms or an alkylphenyl group the alkyl group of which has 7 to 15 carbon atoms and in which χ is 3 to 15 examples of such Compounds are: Nonylphenol, which is condensed with about 9 moles of ethylene oxide per molecule, an alcohol of the coconut type or dodecyl alcohol, which is condensed with about 6 moles of ethylene oxide per molecule or Tallow-type alcohols condensed with about 11 moles of ethylene oxide per molecule. It can also a mixture of these compounds can be used. When using non-biological surface-active Compounds that have a phenyl group in their structure can provide advantages.

Alcohols of the coconut type and tallow type are to be understood as meaning those alcohols which have a chain length similar to those which are derived from coconut _{fatty acids, ie C 0} - u fatty acids or tallow fatty acids, ie C 18 fatty acids. These alcohols can be derived from natural fats or fatty acids, or they can be synthetic or derived from petroleum sources. They are preferably straight-chain alcohols.

The ratio of zwitterionic to nonionic detergent can be used in the inventive Mixtures in the weight range from 9: 1 to 1: 9, preferably in the range from 3: 1 to 1: 3, vary and is in particular 1: 1. Not all non-ionic components are equally effective, and some are less effective effective are expediently used in the proportions preferred to a greater extent. So it is best to use alcohols of the tallow type with 11 moles of ethylene oxide in a ratio to the zwitterionic components from 3: 1 to 1: 3.

The addition of detergent builders to the detergent and cleaning agent according to the invention has only a relatively small effect on their cleaning power compared to polyester and polyamide fabrics, but improves their cleaning power compared to natural fabrics, especially cotton, and the The invention also includes detergents and cleaning agents according to the claims with a content of builders.

This presence of builders is particularly advantageous when washing cotton fabrics, contaminated with material containing clay particles. Suitable roast materials include those known in the art

s Type that are widely used in common detergents and cleaning agents, e.g. B. the alkali metal polyphosphates and aminopolycarboxylates, such as. B. Salts of Nitrilotriacetic acid. These builders can be used in the usual proportions, e.g. B. in such

ίο way that the weight ratio of builder too organic detergent and cleaning agent about 30: 1 up to 1: 5, usually 10: 1 to 1: 4, as already mentioned, show the washing according to the invention and detergents even at relatively low levels

If the builder content is not the disadvantages of "less builder-containing" known agents of this type.

For example, the detergent and cleaning agent according to the invention was effective in low proportions of polyphosphate, especially sodium tripolyphos

zo phat, be strengthened, on the other hand, for one effective enhancement of typical anionic detergents, e.g. alkylbenzenesulfonates or alkyl sulfates, the molar ratio of sodium tripolyphosphate to calcium ion is at least 1: 1 and under practical conditions in hard water normally even about 1.4: 1 to 3: 1. An effective one Reinforcement of the detergents and cleaning agents according to the invention can, however, even then be obtained when the molar ratio is only 1.4 Es it is believed that tripolyphosphate is involved in these at lower ratios, although these are weaker than those at a ratio of 1: 1 determined with aminocarboxylate builders, e.g. B. Sodium nitrilotriaceiai, may be a similar one Effect cannot be achieved, since this apparently, except for the normal ratio of 1: 1, do not chelate.

The washing and cleaning agents according to the invention can, however, also contain complex-forming agents be strengthened, which have a lower chelating power than the polyphosphates and those for Common detergents are not very effective builders. Such substances include: polycarboxylic acids, especially hydroxy-containing polycarboxylic acids,

for example citric acid, tartaric acid, malic acid, Gluconic acid and the like, and their soluble salts. Also to be mentioned are polymeric carboxylic acids and their Salts, e.g. B. polyacrylic acid, polymaleic acid and polyitaconic acid. These substances have the advantage that they are free of nitrogen- or phosphate-containing plant nutrients, which promote the growth of algae in natural Can favor waters into which drains containing the washing waste liquor can be emptied. The mixtures according to the invention can thus it should be assumed that they have little in the way of such Contains plant nutrients and, if desired, no phosphates at all.

Other components that are commonly used in detergent and cleaning agent mixtures, can be contained in the mixtures according to the invention. These include such substances as water-soluble, non-complexing inorganic salts, e.g. orthophosphates, carbonates, sulfates, silicates, Borates and chlorides, especially the alkali metal or ammonium salts; Bleaches such as persalts e.g. B. Sodium perborate or sodium percarbonate other peroxy bleaches e.g. B. the aliphatic and aromatic percarboxylic acids, or organic peroxides;

Activators and / or stabilizers for these bleaches; EiUiTiEe, e.g. proteases, amylases or upases and stabilizers therefor; and the usual minor components, such as perfumes, dyes, haze inhibitors, suds suppressing agents, suds controlling agents, optical brighteners, and the like. The products can be in any conventional physical form, such as grains, bars, briquettes, liquids or pastea

It has surprisingly been found that particularly good triangular removal is obtained if the mixtures according to the invention contain proteolytic enzymes of the type described in Belgian Patent 7 21 730, Table IX, Type!, Which enzymes are deposited under N.CLB numbers have been.

The proteolytic enzymes suitable for use are as in the Belgian one Patent 7 21 730 on page 3 !, Table IX, enzyme type 1, are described. The preferred species for use in the mixtures according to the invention are in same reference p. 27, Table VIII, species 1, variety a; Species IV, variety a; and species VII described. Most preferred are the strains numbered C 372, C 367 and C 370; all of these latter reference names correspond to strains of bacteria listed in The National Collection of Industrial Bacteria, Torry Research Station, Aberdeen, Scotland (N.C.I.B.), have been deposited. All relevant N.GLB. numbers are in the Belgian patent specification 7 21 730 stated. As an example, the N.CLB.numbers of the bacterium strain are given below, which forms the most preferred enzyme species for use in the invention Mixtures are suitable: C 372 corresponds to N.C1.B. 10,317; C 303 corresponds to N.CI.B. 10147; C 367 corresponds to N.C1.B. 10 313, and C 370 corresponds to N.C.I.B. 10315. The full range of N.CLB.-numbers can be found on pages 4, 5 and 6 of the above-mentioned Belgian

Patent specification These enzymes are preferably used in a proportion of 0.01 to 2% by weight of a mixture of 4

Other proteolytic enzymes and / or the amylolytic and polytic enzymes can be found in the preferred proteolytic enzymes described above be included.

The inventive mixtures can be used by washing operations for all types, but their special advantages are in fabric washing most of value for this purpose they may be applied in concentrations such that at least about 2 x 10- ⁵ gram-moles of the mixture of components {a) and (b) per liter of washing liquid are adjusted to about 1 x 10 ~ ² gram moles. When using the preferred components, the usual concentration of components (a) and (b) taken together is within the range from 0.01 to 0.1% by weight. The washing procedure may be performed at any normal washing temperature, for example at about 15 to 100 ⁰ C, in particular about 20 to 95 "C, but are mixtures according to the invention, especially under cold wash conditions, for example, about 20 to 50 ⁰ C, of a value having the washing liquid usually a pH in the range of about 7 to 11, the optimum pH for any given formulation depending, among other things, on the type of builder employed

The following examples illustrate the invention; the percentages given are% by weight.

example 1

3 laundry detergent and cleaning agent mixtures were produced which had the following compositions the first (A) being a conventional mixture for comparison purposes, while the other mixtures are according to the invention.

A. 6th - B. 7th C. 7th - 7th Linear sodium dodecylbenzenesulfonate 4th 37 37 Sodium tallow alkyl sulfate 2.5 - - 7th 5 - 5 Soap (80:20; tallow: coconut oil) 1.5 - 8th - 8th Coconut ethanolamide 37 25th 25th 3- (N-dodecylbenzyl-N, N-dimethylammonio) - 5 1 1 propane-1-sulfonate 8th 0.25 0.25 Nonylphenol - 9 Viol ethylene oxide 25th 2.25 2.25 Coconut alcohol - 6 moles of ethylene oxide 1 Sodium tripolyphosphate 0.25 7.5 7.5 Sodium silicate 2.25 Sodium sulfate Sodium perborate tetrahydrate 7.5 Sodium carboxymethyl cellulose Sodium ethylenediamine tetraacetate Perfume, optical brighteners, proteolytic enzymes and miscellaneous humidity

100%

100%

100%

To evaluate the cleaning effect on common dirt, such as those from shirt collars and -cuffs, samples of untreated (i.e. not treated with regard to crease resistance etc.) cotton, super polyamide and polyester-cotton (P / C-) fabrics at the Krefeld Institute for Washing Research, Germany, using the method known as "WFK Pollution", soils the cloths of these Soiled fabrics were in a miniature washing machine with a 0.2 wt .-% solution of the

the above mixtures for 3 minutes in hard water (258 parts / million as calcium carbonate) at the stated Temperatures washed. Reflection measurements

indicated the extent of soil removal. The results were:

Washing temperature
49 ° C

Cotton super polyamide polyester /
cotton

38 ° C
cotton

Super polyamide

Polyester / cotton

Mixture A 25 18 48 9 11th 28 Mixture B 52 93 75 32 71 46 Mixture C Not checked 36 56 50

To evaluate the ability to remove greasy soil, samples of the the same fabric soiled with the substances listed below and placed in a miniature washing machine washed under the specified conditions with a 0.5% solution of the same mixture. The cleaning achieved was compared by inspection in a test with mixtures in pairs, with 3 replicates taking samples from each of the wash conditions by a group of four panelists were compared, two samples being subjected to the comparison at the same time. Through Appropriate collection of ratings was a numerical assessment of the performance of each blend given, with the higher values indicating better performance; the confidence limits were that indicate the least significant difference (LSD) between ratings. This was the smallest difference with 95% probability of correctness based on the arbitrary variation of the judgments of the same and repeated comparisons. The results were as follows:

spot

tissue

Washing conditions

time

(min) temperature
( ⁰ C)

evaluation

comparison

AWAY

LSD

Motor sump oil polyester / cotton 10 60 -2.1 +0.7

Lipstick polyester / cotton 5 38 -2.6 +2.1

Lipstick cotton 5 38 -1.6 +2.0

+ 0.7 + 1.5 not tested

0.6 1.0 1.5

Similar performance is obtained when the 3- (N-dodecylbenzyl-N, N-dimethylammonio) propane isulfonate is replaced by the corresponding 4-substituted n-butane-1-sulfonate.

Example 2

The ability of the mixtures according to the invention to remove clayey soils from cotton fabric when reinforced with a low proportion of polyphosphate is illustrated by the following experiment

A BaumwoH terry towel was soiled with ground (40 microns or smaller) garden soil so that its reflection was reduced to about 50% compared to that of the pure fabric, and sample rags were made of the soiled fabric. These were in a miniature washing machine in 03 % solutions of the mixture given below were ^{washed at 40 °} C. for 2 minutes, the water hardness corresponding to 200 parts / million calcium carbonate. The washing test was carried out three times with each detergent and cleaning agent mixture in order to enable the calculation of the confidence limits.

The mixes were as follows:

Linear sodium dodecylbenzene

sulfonate 8.5 -

Sodium tallow alkyl sulfate 5.7 -

Soap (80:20 tallow / coconut oil) 3.7 3- (N-dodecylbenzyl-N, N-dimethyl-

arnmonio) propane-l- sulfonate - 50

so coconut oil6Mol

Ethylene oxide - 5.0 Sodium tripolyphosphate 45.6 5.0 Sodium Silicate 8.0 - Sodium sulfate 11.0 25.0 Sodium bicarbonate - 25.0 Sodium carboxymethyl cellulose 13 5.0 Moisture, miscellaneous 16.0 30.0

The washed cloths were dried and the reflectance values were determined. The results were the

the following, where the “least significant difference” (LSD) is defined as in Example 1

Composition D%)

reflection LSD

643 10Own%

663

709610/200

ίο

The reflection is plotted on a scale, with the unpolluted rag 100% and the one not washed, soiled rags mean 0%.

The mixtures of the invention thus removed, albeit a low level of organic Contained detergent and only about '/ < > The polyphosphate, clayey dirt just as well as a full Laundry detergent and cleaning agent mixture containing builders based on common anionic detergents.

Example 3
The following mixes were made:

F. 6th - 5 G 7th 5 H 7th 5 1 7th K 6th - L. 7th Linear sodium dodecylbenzenesulfonate 4th 8th 8th 8th 4th N atrium tallow alkyl sulfate 2.5 - 25th 7th 25th 7th 25th 7th 2.5 - 7th Soap (80:20 tallow / coconut oil) 1.5 37 1 37 1 10 1 10 1.5 10 - 10 Coconut ethanolamide _ 2.5 - 2.5 2.5 27 27 - 27 3- (N-dodecylbenzyldimethylammonio) - 5 propane-1-sulfonate 7.5 7.5 Rest*) 8th _ Coconut alcohol - 6 moles of ethylene oxide 25th _ Sodium tripolyphosphate 1 Sodium citrate 2.5 _ Sodium silicate Sodium sulfate 7.5 Rest') Rest*) Sodium perborate tetrahydrate Sodium carboxymethyl cellulose Perfume, optical brighteners, various Impurities, etc. humidity

100

100

100

100

100

·) In these cases the moisture content is nominal, but the concentrations of the solutions used for the cleaning tests were based on these nominal mixtures, so that the values of the active components were exactly comparable

The test pieces made of superpolyamide, cotton and polyester / cotton fabrics, which, as in Example 1 indicated, were soiled, and of clay-soiled cotton fabric, which, as in Example 2 indicated was soiled were washed in a miniature washing machine in solutions containing 0.2 or Contained 0.5% by weight of the above blends in hard water (258 parts / million as potassium carbonate), the washing time being 10 minutes at 38 ° C. she were then rinsed and dried by reflectance measurements in ultraviolet white light on the Soiled fabric, your soiled fabric and the washed fabric was the extent of the Soil Removal Determined It should be noted that the mixtures containing 37% polyphosphate at one

Concentration of 0.5% in the hard water used in the test contained full builder, but less builder at a concentration of 0.2%.
The results are given in the table below.

Mixture% dirt removal

Concentration 03% super tree

poly wool

amide

Polyester / cotton

Cotton / clay Concentration 0.2% Super tree

poly wool

amide

Polyester / cotton

Cotton / clay

75
88
83
82
78
82

56
82
65
77
43
80

34 55 36 48 26 48

32
86
75
82
25th
82

50
55
48
66
48
66

27
26th
28
33
25th
39

62 77 64 71 38 75

These results show differences in the rhyme gong effect of the mixtures according to de

Remigang is very good with all blends (clay-soiled cotton - 03% concentration)

w> the derSbicben

and non-ionic (ethanolamide) Aktivdeae

Example 4

The result was a solution with a content of 0.6% by weight of the following detergent and cleaning agent mixture manufactured: s

% By weight

Condensation product of
Coconut alcohol with 6 molar proportions of ethylene oxide 5 ίο dodecylbenzyldimethylammoniopropanesulfonate 5 sodium tripolyphosphate 65 sodium sulfate 10 carboxymethyl cellulose 1.5 moisture and various
Inert materials 12.5

The solution was divided into 2 parts and 1 part became parts / million of a widely used protease added, which is known as "Alcalase", while the other part 20 parts / million of the enzyme from the strain

C 303 (N.C.I.B. 10147) was added; under "Enzyme" is to be understood here as an enzyme preparation that has 1.5 Anson activity units per g.

Cotton test pieces with a blood-milk-Ink- (BMI) stain agents were spotted (commercially available as EMPA no. 116 available), and others with spinach stains were washed in these solutions in a launderometer, charged its container at 20 ⁰ C and has been gradually heated ^{to 6O 0 C within 40 minutes.}

The rags were rinsed and dried and their reflectance values were similar to those of the unwashed Test fabrics compared.

The percent stain removal values were as follows:

Alcalase

Enzyme des
Tribal C 303

BMI patches
Spinach stains

8th
17th

34 33

Claims (1)

Patent claims: 1. Detergents and cleaning agents with a content on a nonionic surfactant s based on polyethoxy compounds and a sulfobetaine, characterized in that the sulfobetaine one of the general formula