DE1767358A1 - Easily biodegradable, non-toxic detergent and cleaning agent - Google Patents

Description

"Easily biodegradable, non-toxic laundry and

Cleaning supplies"

Modern detergent and cleaning agent compositions are required to be biologically fast in the wastewater and be completely dismantled. This requirement is generally considered to be met when the Washing active substances predominantly straight-chain alkyl residues contain. Furthermore, the washing raw materials should have a low toxicity to fish and those living in the water, show the fish as food serving small organisms. Most of the known washing active substances meet this requirement to a sufficient extent, especially because of their concentration In the wastewater under normal conditions it is so low that for this reason alone there is no risk is. Under unfavorable conditions, for example with high wastewater pollution and simultaneous low water flow of the However, streams and rivers can reduce the concentration of Wasehrohstoffo Rise so high in the wastewater that the harmful or even lethal dose is reached and the fish pond is endangered. Ea The task was therefore to develop detergents which, in addition to having a high level of rinsing effect and good biodegradability,

109815/1951

BAD OB (GINAl

176735C

ability have such a low toxicity that a higher concentration in the wastewater does not result in any damage to the fish population.

The invention relates to a non-toxic, easily biodegradable washing active substance, consisting of a synergistic mixture of alkali or ammonium salts or salts of organic bases of the following aliphatic straight-chain sulfonic acids, each containing 10 to 20 carbon atoms, with at least one secondary sulfonic acid group:

a) 30 to 80 wt .- $ of a monosulfonic acid with a

olefinic double bond in β, fr or έ position to the sulfonic acid group,

b) 20 to 70 wt -.% of a monosulfonic acid in a (2-, JF ", o- or ε position located to the sulfonic acid hydroxyl group,

c) 2 to 15 wt -.% of a disulfonic acid with two

secondary sulfonic acid groups arranged in the / ^ - or ^ -position to one another, with an olefinic double bond or a hydroxyl group being in the β-, f ~ or ί-position to one of the two sulfonic acid groups.

Components a, b and c are abbreviated below as alkene sulfonates, hydroxyalkane sulfonates and disulfonates.

The alkene sulfonic acids (component a) can be represented by the following formulas:

109815/1951 -3-

ßAD ORIGINAL

176735C

1) CH ₅ - (CH ₂ ) _X -CH ₂ -CH ₂ -CH = CH-CH- (CH ₂ ) -

SO ₅ H

2) CH, - (CH ₀ ) _Y -CH ₀ -CH = CH-CH ₀ -CH- (CH ₀ ) _V -CH,

SO ₅ H

3) CH ₅ - (CH ₂ ) _x -CH = CH-CH ₂ -CH ₂ -CH- (CH ₂ ) _y -CH ₅

SO ₃ H

x = 0 to 10, y = 0 to 8, χ + y = 3 to

The following structures result for the hydroxyalkanesulfonates (component b):

4) CH, - (CH _O ) -CH ₀ -CH ₀ -CH-CH-CH- (Ch ₀ ), -CH-,

OH SO ₅ H

5) CH ₅ - (CH ₂ ) _X -CH ₂ -CH ₂ -CH-CH ₂ -CH- (CH ₂ ) -CH ₅

OH SO ₃ H

6) CH ₅ - (CH ₂ ) _X -CH ₂ -CH-CH ₂ -CH ₂ -CH- (CH ₂ ) -CH ₅

OH SO ₃ H

OH SO ₃ H

x = 0 to 10, y = 0 to 8, χ + y = 3 to

109815/1951

ORiGiNAL INSPECTED

176735C

The disulfonates (component c) can essentially be represented by the following formulas:

8) CH ₃ - (CHg) ₂ -CH ₂ -CH ₂ -CH = CH-CH - CH - (CH ₂ ) -CH,

SO, H SO, H

9) CH ₃ - (CHg) ₂ -CH ₂ -CH = CH-CH ₂ -CH - CH - (CHg) --CH ₃

SO ₃ H SO ₃ H

10) CH ₃ - (CHg) ₂ -CHg-CII = CH-CH -CHg-CH- (CH ₂ L-CH ₃

SO ₃ II SO ₃ H

11) CH ₃ - (CH ₂ J ₂ -CH = CH-CH ₂ -CH - CH ₃ -CH - (CH ₂ )

SO, H SO, H

3 3

12) CH, - (CH ₀ ) -CH _o -CH _o -CH _o -CH-CH - CH -

J d It d d d \ I I

OH SO ₃ H SO ₃ H

13) CH, - (CH ₀ ) -CH ₀ -CH ₀ -CH-CH ₀ -CH - CH - (CH) -CH,

J <- Z d d I d \ 1 YP

OH SO H SO ^ H

14) CH, - (CHg) ₂ -CH ₂ -CH-CH ₂ -CH ₂ -CH - CH - (CH) -CH

OH S0, H S0, H

15) CH, - (CH ₀ ), -CH ₀ -CH ₀ -CH -CH - CH ₀ -CH - (CIl) "- CH,

^w J c Z ti C. 1 t d. I Jf J?

OH SOH SO, H

16) CH, - (CHg) ₂ -CH ₂ -CH-CH ₂ -CH - CH ₃ -CH - (CH) -CH ₃

OH SO ₃ II SO ₃ H

17) CH ₃ - (CHg) ₂ -CH-CH ₂ -CH ₂ -CH - CH ₂ -CH - (CH) -CH ₃

OH SO ₃ II SO ₃ II

y = ο to 8, z = (x-l) = 0 to 9, y + ζ = 2 to

109815/1951 " ⁵ "

OFUGINAL INSPECTED

" ⁵ " 176735C

The abovementioned washing active substances can be obtained in a known manner. The isomer mixture consisting of secondary alkene sulfonates can be obtained, for example, by sulfonating straight-chain olefins containing 10 to 20 carbon atoms and an internal double bond with sulfur trioxide and / or chlorosulfonic acid, acid hydrolysis of the sulfonation products at temperatures above 150 ^° C. and subsequent neutralization. Secondary hydroxyalkanesulfonates-. can be obtained, for example, by hydroxylation of the aforementioned secondary alkene sulfonates. Of hydroxy-rich mixtures are also obtained when, Olefinsulfonierungsprodukte produced using sulfur trioxide or chlorosulfonic acid as described above is hydrolyzed in an alkaline medium at temperatures between 60 and 200 ⁰ C. The mixtures of secondary alkene disulphonic acids and hydroxyalkane disulphonic acids are formed when the secondary alkene monosulphonic acids are reacted with sulfur trioxide. "

The position of the sulfonate group within the molecule depends of the nature of those used as starting materials for the sulfonation Olefins, i.e. their chain length and the position of the olefinic double bond within the hydrocarbon chain. Regardless of the chain length of the hydrocarbon radical and the position of the double bond, the isomers are in one given distribution, which moves essentially within the following limits.

109815/1951 - ⁶ -

BATH ORIGINAL

"176735C

a) Alkene sulfonate (based on 100 % ):

Formula 1 30 to 80 %

Formula 2 10 to 50 %

Formula 3 5 to 20 %

b) Hydroxyalkanesulfonate (based on 100 % ):

Formula 4 5 to 20 %

Formula 5 40 to 80 #

Formula 6 20 to 40 %

Formula 7 2 to 20 %

c) Disulfonates (based on 100 % ):

Formula 8 10 to 40 %

Formula 9 5 to 30 #

Formulas 10 and 11 a total of 5 to 20 %

Formula 12 2 to 10 %

Formula 13 £ 10 to £ 30

Formulas 14 to 17 in total 10 to 40 %

The mixtures consisting of secondary alkene sulfonate, secondary hydroxyalkane sulfonate and secondary disulfonate can be hydrocarbon radicals have the same or different chain length. The hydrocarbon radicals should preferably be 12 to 18 carbon contain atoms.

The washing raw materials mentioned are in the form of their sodium, potassium and ammonium salts or as salts of organic bases, such as mono-, di- or triethanolamine, morpholn or N-methy1-morpholn before. The salts of organic bases are particularly suitable for the production of cleaning agents that contain organic, Contains solvents which are immiscible with water.

109815/1951. _7th

BATH ORIGINAL

The washing raw materials are preferably used in detergents and cleaning agents used j the at least one additional inorganic or organic cleaning or cleaning enhancement active compound included.

Examples of inorganic cleaning salts that can be contained in the washing and cleaning agents are acidic and neutral pyrophosphates, such as tetrasodium pyrophosphate, dina- λ trium dihydrogen pyrophosphate and the corresponding potassium salts, pentasodium triphosphate, pentapotassium triphosphate and the mixtures of the aforementioned phosphates. Furthermore, higher-density phosphates, such as tri- or polymetaphosphates, can be present. Other suitable inorganic cleaning salts are bicarbonates, carbonates, silicates, borates and sulfates of alkali metals, especially sodium.

Examples of organic cleaning salts are the sodium, potassium or ammonium salts of citric acid, Aminotriessig- ™ acid, ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, triethylenetetraaminohexaacetic acid and their higher Homologues, ethylenediaminohydroxyethane triacetic acid, aminotri (methylenephosphonic acid), Ethylenediaminotetra (methylenephosphonic acid), l-hydroxyethane- ^ l-diphosphonic acid, methylenediphosphonic acid and the higher homologues of the polyphosphonic acids mentioned.

- 8 109815/1951

BATH ORIGINAL

176735C

As mixture components, can as far as it concerns light-duty detergent, manual dishwashing detergents and hand washing preparations, foam stabilizers such as Fettsä'uremono- and -dialkylolamide and skin protection substances and iJbei ⁿ degreasing agent be present. Agents intended for use in washing machines instead contain foam inhibitors, for example saturated fatty acids or their alkali soaps with 20 to 2 ^ l carbon atoms or triazine derivatives, which are produced by reacting 1 mole of cyanuric chloride with 2 to 3 moles of an aliphatic, straight-chain, branched or cyclic primary monoamine are available. Furthermore, the agents can contain enzymes which are obtained from digestive enzymes, yeasts or bacterial strains and with which contaminants containing protein, fat and starch are broken down by fermentation. Alkali salts of cellulose glycolic acid, polyacrylic acid and their copolymers and other polyanionic polymers are suitable as graying-preventing additives.

The agents can also be used as compounds with bleaching agents Effect contain, such as perborates, percarbonates, perpyrpphosphates, persilicates, persulfates, urea perhydrate and organic Peracids or peroxides. Sodium perborate tetrahydrate is preferred used. To stabilize the per compound, the agents can contain magnesium silicate.

- 9 109815/1951

BATH ORIGINAL

Liquid MLfcfcel can also contain hydrotopic substances and Solutions contain, as alkali salts of the benzene, Toluol or xyloLsulfonic acid, urea, glycerine, polyglycerine, Di- or TrlgLyool, PolyathyLengLycoL, Ethanol, L-PropanoL and ether alcohols. Detergent for hard Surfaces can have a content of mineral friction materials, such as quartz, feLdspar or marble powder, which have an abrasive effect Kunr.th. irz granules and active chlorine compounds, such as sodium Jj

dichloroisocyanurate.

Except that of alkene sulfonate, hydroxy sulfonate and disulfonate at; dividing mixture can (ILe V / ash and cleaning agents also still further known anioriLsohe and / or non-ionic washing act ivoiibs dance with a good logical degradation count and low:;! · Toxicity included. Anionic compounds, dLe these Own property are in particular fatty acid alkali soaps of chain length C.ρ - C ^ ,,, primary and secondary alkyl sulfates j

of chain length C. _o - C, ο as well as primary and secondary alkyl polygtyao ether sulfates with 10 to l8 carbon atoms Lm alkyl radical and 1 to 5 ethylene GlyooLäbhergruppori. In any case, the agents can contain minor amounts, ie up to about ¹ % of the amount of knpLLLaractlver V / asohactive substance, including those anionic, second-lontic or nLohtLonischeiii V / asohaktLvniibstanzen that are biologically good der 7oraiu> Hobzung that these V / a ;; c.haktl '/ i; ub; dance only Ln unt-ai'geordn-'t -.' r Mengf) are anvienerul,

109815/196! -io-

BAD ORiGiNAL

176735C

If your concentrate is in the wastewater, even in unfavorable cases below the critical area. These washing active substances include n-alkylbenzenesulfonates, the alkyl chain of which is 8 bin Contains a maximum of 1J5 carbon atoms and n-alkanesulfonates, for example by sulfoxidation or sulfochlorination from n-paraffins and subsequent saponification or neutralization of the sulfonation products or by disulfite addition to primary or secondary n-olefins are available. There are also the reaction products of propane sultone or butane sultone with 8 to 22 carbon atoms containing alcohols, amines and fatty acids as well as those of fatty acids having 8 to 22 carbon atoms derived ot-sulfo fatty acid esters, monoglyceride sulfates and sulfosuccinic acid esters. High molecular weight betaines, sulfate betaines and sulfobetaines are suitable as zwitterionic washing active substances. Suitable nonionic washing active substances are alkyl polyglyeol ethers, obtained from saturated or unsaturated fatty alcohols of natural origin or synthetic alcohols and 10 to 18 carbon atoms in the alkyl chain as well as H to 12 ethylene glycol ether groups.

Detergents and cleaning agents of the specified composition have a number of advantages over known agents. Their low toxicity towards fish and small organisms in the water should be emphasized in the first place. In this respect they surpass all comparable detergent compositions with a content of washing raw materials of the sulfate or sulfonate type. Insofar as the toxicity of known synthetic washing active substances with a comparable cleaning effect in the same size range

109815/1951

- Il BAD ORIGINAL

176735C

Order is, as in the case of tetrapropylenebenzenesulfonate or the alkylphenol polyglycol ethers, the latter are in contrast to the Compositions according to the invention are not or only slightly biodegradable in wastewater. In their cleaning effect and water solubility, especially in cold or moderately warm water and in their resistance to hardness builders and hydrolyzing agents, the agents according to the invention are the detergents of the older type, i.e. those that are mainly based on soap and fatty alcohol sulfates and which also have very favorable physiological properties, are considerably superior. Because of their good solubility in cold water, the sodium salts of the mixtures according to the invention are particularly suitable excellent for the production of concentrated liquid preparations as well as cold detergents. The well-known property of anionic Washing active substances, in particular those of the sulfate and sulfonate type, to inactivate enzymes in whole or in part, is at the compositions according to the invention are only very weakly pronounced, so that they can be used with advantage and without significant losses Enzyme activity in enzymatic pre- or heavy-duty detergents can be used.

The following are some compositions for the present invention Detergents, dishwashing detergents and cleaning agents are listed. However, the invention is not limited to the following mixtures, rather, these can be modified in many ways or by the additional items listed in the description.

109815/1951 - 12 -

8AD ORIGINAL

176735C

fabrics are supplemented. Further, the anionic detergent active substances, up to ^ O wt -.% Of n-alkylbenzene sulfonates / n-alkane sulfonates, od-sulfo fatty acid esters, sulfosuccinic acid esters, and Alkylglycerlnäthersulfonate Acylglycerinestersulfonate be replaced. As far as liquid preparations are concerned, the anionic washing active substances can advantageously be used in the form of the mono-, di- or triethanolammonium salts.

109815 / 19S1

BATH ORIGINAL

- 13 - 176735C

1 »Powdery, low-foaming detergent: 3 15 % sec. Alkene sulfonate, 2 15 % sec. Hydroxyalkanesulfonate, 0.1-5 % sec. Disulfonate,

Q- 5 % alkyl poly glycol ether (C ₁₂ -C 4 alkyl, 5 to 10 ethylene glycol ether groups). 0 5 % soap C ₁₂ -C ^,

0.2 - 8 % of a foam suppressant from the class. \ the fatty acids or their alkali soaps with 20-2h carbon atoms or triazine derivatives, obtainable by reacting 1 mole of cyanuric chloride with 2-3 moles of an alkylamine with 4 to 20 carbon atoms,

10 - 50 # of a condensed alkali metal phosphate from the. Class of pyro- or tripolyphosphates,

0 - 20 % complexing agents from the class of alkali salts of aminopolycarboxylic acids, aminoalkylenepolyphosphonic acids and hydroxyalkanephosphonic acids,

Sodium silicate, etc.

Sodium perborate tetrahydrate,

Enzyme,

an optical brightening agent from the class of diamiriontilbene disulfonic acid derivatives,

an inorganic salt from the class of carbonates, bicarbonates, borates, sulfates and Alkali metal chlorides,

0.5 - ^l \% magnesium silicate, 0.5 - 3 ^c / o sodium oilulose glycolate.

109816/1861

BATH ORIGINAL

1 05 - 5th 10 1 - 35 0 - 5th 0, - 1 0, - 30

176735C

2. Powdered mild detergent:

4 - 30 % sec. Alkanesulfonate, 3 - 30 % sec. Hydroxyalkanesulfonatej 0.2-10 # sec. Disulfonate, 0-10 # alkyl polyglycol ether sulfate

1-5 ethylene glycol ether groups),

_0-20 % alkyl polyglycol ether (C _{1 ()} -C 18 -alkyl, 5-12 ethylene glycol ether groups) j

0 - 5 % fatty acid ethanolamide or -dläthanolarald ^ 0 - 10 % alkali tripolyphosphate,

0 - 20 % complexing agent from the class of alkali salts

of aminotriacetic acid, ethylenediaminotetraacetic acid, hydroxyethane diphosphonic acid and amino alkylenephosphonic acids,

3 - 30 % sodium sulfate.

3. Soaking and pre-wash detergent:

2 - 8 % sec, alkene sulfonate,

1 - 8 % sec. Hydroxyalkanesulfonate, 0.1-2 % sec. Disulfonate,

0 - 3 % alkyl polyglycol ether (C ₁₂ -C ₁ Q-AlKyI,

5-12 ethylene glycol ether groups), - 50 % soda,

1 - 5 % water glass,

0-5 % magnesium silicate, 0-5 % enzyme.

109815/1951 -W-

BATH ORIGINAL

4.Liquid detergent:

l [ - 40 % sec. Alkene sulfonate, 3 - 30 $ sec. Hydroxyalkanesulfonate, 0.2-8 # sec. Disulfonate, 0-10 % alkyl polyglycol ether sulfate

1-5 ethylene glycol ether groups),

0.5 - 5 % fatty acid amide glycol ether condensate

(C ₁₀ -C ₁ g-alkyl, 1-10 ethylene glycol ether groups),

2 - 10 % solubilizer from the class of alkali salts \

benzene, toluene or xylene sulfonic acid,

0 - 20 % neutral or acidic potassium pyrophosphate,

0 - 10 % organic solvents from the class of Cp-C, alcohols and ether alcohols,

Remainder water, fragrances, dyes.

5. Liquid detergent and cleaning agent: h - k0% sec. Alkene sulfonate,

3 - 30 % sec. Hydroxyalkanesulfonate,

0.2 - 10 % sec. Disulfonate, "

0 - 10 % alkyl polyglycol ether sulfate (Cn-C ^ -alkyl, 1-5 ethylene glycol ether groups),

0 - 10 % fatty acid amide glycol ether condensate

(C.Q-CjQ fatty acid amide, 1 to 10 ethylene glycol ether groups) ,

0 - 10 % alkyl polyglycol ether (C ₁₂ -C ₁₈ alkyl, 5-12 ethylene glycol ether groups),

0 - 30 % organic solvents from the class of Cp-C, alcohols and ether alcohols,

Remainder water, fragrances, dyes, preservatives.

109815/1951

- 16 -

ßAD ORIGINAL

176735C

6. Abrasives:

0.5 - 2 % sec. Alkene sulfonate,

0, ^ - 2% sec. Hydroxyalkanesulfonate,

0.02 - 0.5 % sec. Disulfonate,

0.5 - 10 % soda, sodium sesquicarbonate, sodium carbonate,

0 5 % ortho-, pyro- or polyphosphates

- 95 ■% abrasives,

0 2 % sodium dichloroisocyanurate,

P 0.1-5 % sodium sulfate.

7 »Cold washing and bleaching agents:

3 - 15 fo sec. Alkene sulfonate, 2-15 % sec. Hydroxyalkanesulfonate, 0.1-5 $ sec. Disulfonate,

0 - 10 % alkyl polyglycol ether (Cg-C ^ g-alkyl, 5 to 10 ethylene glycol ether groups),

- 50 % of a condensed alkali metal phosphate from the ^ class of pyro- or tripolyphosphates,

0 - 25 % complexing agents from the class of alkali salts of aminopolycarboxylic acids, aminoalkylenepolyphosphonic acids and hydroxyalkanephosphonic acids,

Sodium silicate,
Sodium dichloroisocyanurate, optical brightener,

an inorganic salt from the class of carbonates, bicarbonates, borates * sulfates and Alkali metal chlorides.

109815/1951 - 17 -

BATH ORIGINAL

0 1 - 5th 1 1 - 20th O, - 2 O, - 30

example 1

The sulfonate mixture in the form of the sodium salts produced from Δ-olefins of chain length C ₁ to C _{17 used in the following example consisted essentially of:}

24 % alkene sulfonate of formula 1

10 % alkali sulfonate of formula 2

4 % alkene sulfonate of formula 3

4 % hydroxyalkanesulfonate of formula 4

30 % hydroxyalkanesulfonate of the formula 5 '" ύ

15 % hydroxyalkanesulfonate of formula 6

6 % hydroxyalkanesulfonate of formula 7

3 % disulfonate of formulas 8 to 11

4 % disulfonate of formulas 12 to 17

In the formulas mean:

χ = 5 to 10, y = 0 to 1 and ζ = 4 to 9.

. Hydroxyalkansulforiat% and 1.4 Gev /.-^ Dinulfonat, sov - produced a liquid detergent in this Gemisch'wurde that a total of 20 wt -.% Sulfonate, ie, 7.6 wt .->1> alkene sulfonate, a 11 wt 0.1% by weight of sodium betizoate as a preservative. The hergontellte from this agent mLT cleaning solution containing 0.5 wt -.% Bulfon.it-V / .mischrohr, toff was used for washing dishes. Dij behinlelton objects v / areri ol wall-free cleaned. Dar »Center L was na oh the Vorrichriften the" ordinance for Doufc'iühon Dijberg "ntiongoi>Gtz" (Amtliohor German Detergentiente "t) gyprtift, where as the percent decrease in methylene blue-acti '/ s iJubnt-mz be.'itimmt v / urde. Dio To-

10 98 1 5/1 9S1 - iö -

BATH ORIGINAL

-is- ¹ 176735C

xicity was determined against Daphnia and fish (Goldorfer). For comparison, detergents were used which, instead of the above surfactant mixture, contained the same amount by weight of known anionic and nonionic washing active substances. The anionic compounds were also used as sodium salts. The percentage degradation of the nonionic compounds was determined using the WICKBOID pyrrolidine dithiocarbamate method. The results are compiled in the following table. The designation DL indicates the highest tolerable amount of washing raw material in mg / l, while Wjiqq ^{(denotes the} lowest concentration of washing raw material in mg / l at which all daphnia die within 2 hours and all fish within 48 hours.

109815/1951

co

(O

ro

Washing active substance DL Toxicity against
Daphnia
0 ^DL i00 enover
fishing
DL ₀ DL ₁₀₀ 20th Biolog. Dismantling Mixture according to example 1 40 50 12th 3.5 98 "Yes a) C ₁₄ -C ₁ Q βί olefin sulfonate 3, 5 17 1.5 3.5 97 Io b) C ^ -Cig alkane sulfonate ("sulfoxldate") 2 5 1.5 2 95 ⁰ Jo c) Petroleum sulfonate 1 10 0.5 5 30 <7o d) n-dodecylbenzenesulfonate 5 15th 3 15th 89 ⁰ Jo e) Tetrapropylene benzene sulfonate 15th 35 11 12th 8 "Jo O Cj2-C-14 fatty alcohol sulfate 5 23 8th 12th 98 Io G) C ₁₂ -C ₁₄ alcohol triglycol ether sulfate 10 27 4th 8th 97 ⁰ Jo W. Nonylphenol nonaglycol ether 5 50 5 6th 7 ⁰ Io i) Coconut fatty alcohol nonaglycol ether 5 10 4th 25th 97 ⁰ Js k) Tall oil soap 36 48 17th 100 °? ₀

CD GG

cn

176735C

The table shows that the mixtures according to the invention are considerably less toxic than the other synthetic detergent raw materials. As far as the toxicity is known synthetic detergent raw materials (comparison substances e and i) are of the same order of magnitude, but this is biological Completely inadequate degradability. The beneficial biological properties of the mixtures according to the invention are only achieved or exceeded by the soap, but the soap has various technical disadvantages, among which the hardness sensitivity, low detergency, moderate solubility and relatively high alkalinity should be emphasized and on the basis of which they are inferior to the agents according to the invention in numerous fields of application.

Example 2

In the composition according to Example 1 were J5 wt -.% Alkane sulfonate, 5 wt .- # hydroxyalkanesulfonate and 0.5 wt -.% Disulfonate replaced by the same amount of each Cp-Cn-Cocosfettalkoholsulfat (Na salt). The detergency and the foaming of the rinse were thereby increased even by about 15%, while the toxicity of the solutions to daphnia and fish only very slightly ie, increased by less than 10 fo.

- 21 -

109815/1951 ORIGINAL BATHROOM

Example 3

One made from mixtures of olefins of chain length 'C, p-C, Q Sulphonate mixture had the following composition:

24 % alkene sulfonate of formula 1

14% alkene sulfonate of the formula 2

6 % alkene sulfonate of formula 3

3 % hydroxyalkanesulfonate of formula 4

32 % hydroxyalkanesulfonate of Formula 5M

12 % hydroxyalkanesulfonate of formula 6

3 $> Hydroxyalkanesulfonate of the formula 7

3 % disulfonate of formulas 8 to 11

3 % disulfonate of formulas 12 to 17

In the formulas mean:

χ = 2 to 10, y = 0 to 9, x + y = 5 to 11, yi-z = 4 to

Using the above sulfonates, eLn White detergent produced, which - stated in wt .- <£ -

3.5 % Ha-alkene sulphonate, 4 % Na hydroxyalkanesulphonate and 0.5% Na disulphonate, 3 % Na soap from coconut and tallow fatty acids and behenic acid, 2 % technical reacted with 10 mol of ethylene oxide. Oleyl alcohol, 40% Pentana tr Lumtri phosphate, P ^c>, "Na tr Lumperborat, 3% MagnesiumsLLLkat, f)% NatrLumsLlikafc, 0.5 $ sodium äthyLendiaminotetraazetat, 2 '/> NafcrLumoelLulonoglynolat further optical brighteners, perfumes, sodium sulfate and water reveals ;. Dosen MitteL is used in a concentration of 7 * 5 g / L for washing soiled table, body and bed linen. The laundry is completely clean. The surfactant mixture is based on the known ones

109815/1951 - 22 -

BATH ORIGINAL

Methods for degradability and toxicity to fish and daphnia examined. It turned out to be very readily biodegradable and was also in comparatively high concentrations relatively nontoxic.

The following table shows some formulations for washing and cleaning agents according to the invention for the following areas of application compiled:

Example h low-foam heavy duty detergent

¹¹ 5 cold detergent

¹¹ 6 River Ig detergent

¹¹ 7 detergent for wool

¹¹ 8 Soaking Agents

"9 low-foam detergent for colored laundry

"10 liquid dishwashing detergent

"11 Cleaner for coarse soiling

"12 abrasives.

The alkene sulfonato, hydroxyalkane sulfonate and Dlsulfonate produced from olefin mixtures of chain length Cp to Cq correspond to the formulas 1 to 17 * where χ = 2 to 10, y = 0 to 9, xi-y - 5 to II and ζ = k to 10. The components A to F and H to K listed in the table were present as HatrLuimjalzu. The pyrophosphate (constituent L) was used in example ¹ I as KalumsuLz, in all other examples as NatrLumaaLi. A preparation Maxataso ^ der obtained from Baoll-Luu subtlhi served as the enzyme (ingredient R)

109815/1951 - 23 -

BATH ORIGINAL

■ 25-176735C

Koninklijke Nederlandsche Gist en Spiritusfabriek N.V., Delft, with an activity of 100,000 LVU / ß. With the show dampening agent (Component U) is a reaction product of 1 mol of cyanuric chloride with 2.7 mol of a pri: mär n-alkylamine of chain length Cq-C.q.

The other ingredients listed under Y are:

Example 6 Sodium Toluene Sulphonate,

Examples 7 and 10 coconut fatty acid diethanolamide, Example 12 Quartz flour.

109815/1951

BATH ORIGINAL

O
CO

approx

co

ro

VJl

L-.

A) B) C)

D) E)

component

C ₁ 2-C28 alkene sulfonate, Ci2-Ci3-hydroxyalkane sulfonate

C12-Ci8 disulfonate

r.-Dodecylbenzenesulibnate

Cj ₄ -C _i 7 alkali sulfoaate

3
3.5

0.4 3.1

Examples (data in wt .- ^ o)
7 8 9 10

11

6.2 2.2 1.6

10

16

1
1.3

0.2
0.5

3.0

4.5
0.4

8.5
5.5
1.0
5

2.5
3.2
0.3

12th

0.8
1.3
0.2

F) Coconut alcohol iglycol ether sulfate (2 AO) ϊ 2.3 - - - - 4th - I. - G) Oley alcohol polyglycol ether (10 AO) 2 4th - 5 - 3.1 - - - H) C ₁₂ -C ₁₈ soap 3 - - - - 4th - - - I) C0Q-C22 soap - - - - - ' 2 - - - K) Tripolyphosphate 10 20th - - - 45 - 10 - Pyrophüsphat '- - 20th - 20th 8th - 2 5 M) soda - 15th - - 35 - - 45 - N) Sodium silicate 5 5 - - 5 3 - 20th 1.9 0) Sodium sulfate 4.4 - - 45 18th 5.5 0.4 1.2 - P) Narrium perborate 25th - * - . - - - - Q) Magnesium silicate 3 - - - 3 - - - - R) enzyme 0.6 - - - 1 0.5 - - - S) Na cellulose glycolate 1.5 - - - 2 2.5 - - - T) Na-aminotriacetate 26th 20th 1 2.5 - 10 - - - U) Shock absorption 0.4 - - - - 0.2 - - - V) water 8.5 7.9 57.2 14.5 13th 8.3 72 14.3 4th W) Dichloroisocyanurate * 15th - - - - - 1.0 0.1 X) Dye, fragrance, opt. Brightener 0.6 0.8 0.3 - - - 0.1 0.1 86 Y) Others 6.5 δ - • 3.5 -

CiJ ^φ co »

a * - 176735D

15th

Example 13

In the following example an olefin sulfonate mixture was used, that from secondary olefins with 13 to 17 carbon atoms and one statistically distributed across the carbon chain Double bond had been established. That in the form of sodium salts Sulphonatgtimlsoh used pointed in the vrcjent Liehen the the following composition:

25 J * »Alkensulforiate der B'ormel L

15 ^c /> alkene sulphate of formula 2

5 ^c j & alkene sulfonate of formula 3

5 ) (} Hydroxya lkansulfona t of the formula ¹ I.

25 ¹ Yes Hydroxya Ikansu Lf ona b of Formula ¹ J

10 $ Hydroxya Ikansu Lf ona b der B'ormel 6 ·.

5 i> Hydroxya lkansulfona b of the formula 7

5 <6 disulfonate of formulas 8 to H.

5 # disulfonate of formulas 12 to 17.

In the formulas mean

χ = 2 to 10, y «0 to 5 * ζ - 2 to 9, χ + y β 5 to 9,. y + ζ β 4 to 8.

- 24 b 10981671951

BATH ORIGINAL

Henkel & Cie GmbH - ßH b - 176 7 35 C

Patent department

D 15368 λ ι

A washing and cleaning solution prepared from this mixture had a content of

1 # suif onate 1.5 0.5 # Ά sodium pyrophosphate sodium sulfate

and was used for dishwashing, for washing fabrics made of synthetic fibers and as a household cleaner. The treated Items were cleaned perfectly. The toxicity test or the determination of the biodegradability resulted in the following fourth:

Daphnia DL _Q ~ ^l ij ^DL loo = fish DL ₀ ■ = 15 ^DL loo ⁼ biodegradation = 98 &.

1.09815 / 1951

BATH ORIGINAL

Claims (11)

Claims 1. Non-toxic, easily biodegradable washing active substance, consisting of a synergistic mixture of the alkali or ammonium salts or salts of organic bases of the following aliphatic straight-chain, in each case 10 to 20 carbon atoms containing sulfonic acids with at least one secondary sulfonic acid group: a) ^ O to 80 wt. - <& a monosulfonic acid with a olefinic double bond located in f3, <jf or h position to the sulfonic acid group, % of a monosulfonic acid located in a ft-t £ -t o- or ε-position to the hydroxyl group sulfonic acid group, - b) 20 to 70 wt. c) 2 to 15 Gent .- ^ C of a disulfonic acid with two in SS or "- position to each other arranged secondary Sulfonsä'uregruppen wherein SIEH- in SS, # * - one of the two sulfonic acid groups is an olefinic double bond or a hydroxyl group, or δ position. 2. Non-toxic, easily biodegradable detergent and cleaning agent, characterized in that it contains the mixtures described in claim. 3 · Non-toxic, easily biodegradable cleaning agent according to claim 2, characterized in that there is at least one further inorganic cleaning or cleaning strengthening effect and / or contains organic compound. 109815/1951 - 26 - 8AD ORIGINAL 176735C 18 4. Means according to claim 3 »characterized in that it is at least efn cleaning salt from the class of condensed phosphates, carbonates, silicates, sulfates and borates of alkali metals contains. 5. Means according to claim 3 and 4, characterized in that there is at least one complexing salt from the class of sodium, potassium and ammonium salts of aminopolycarboxylic acids, Aminoalkanepolyphosphonic acids, hydroxyalkanepolyphosphdn- WL contains acids and alkane polyphosphonic acids. 6. Means after one or more of the before? named claims, characterized by a content of enzymes. 7 Means according to one or more of the preceding claims, marked ;. ..turn a number of pale-looking people Active chlorine compounds « 8. Agent according to one or more of the preceding claims., ^ Characterized by a content of alkali soaps of chain length C ₁ O-Cp ₂ . 9 «Means according to one or more of the preceding claims, gekeniiLe :! It is characterized by a content of primary or secondary alkyl sulphates of chain length C. ₀ ~ C, o. 1ÜÜ815 / 1951 BATH ORIGINAL 176735C 10. Agent according to one or more of the preceding claims, characterized by a content of primary or secondary Alkyl polyglycol ether sulfates with 10 to 18 carbon atoms in the alkyl radical and 1 to 5 ethylene glycol ether groups. 11. Agent according to one or more of the preceding claims, characterized by a content which is up to 40 % of the total amount of capillary active washing substance, of bio. Logically degradable compounds from the class of anionic, zwitterionic, cationic and nonionic capillary-active detergent substances. 109316/1961 ORiGlNAL INSPECTED