DE1257339B - Aqueous liquid detergent with a content of cellulose ether carboxylic acid salts - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE Int. Cl .:

German class:

Number:

File number:

Registration date:

ClId

C07c I

..23e-2
jl2q-6 / 0l

1,257,339
H55644IV a / 23e
March 30, 1965
December 28, 1967
July 25, 1968

Display day:

Issue date:

The patent specification corresponds to the patent specification

The invention relates particularly as a cooking detergent suitable, aqueous, cellulose ether carboxylic acid salts containing liquid detergents based on usual detergent constituents which are solid per se and have improved sedimentation behavior.

Liquid mild detergents have been known for a long time and are already being sold. It has However, it has so far proven difficult to be suitable for hot laundry and to improve the dirt-carrying capacity E. Manufacture detergents containing cellulose glycolic acid salts, in which the settling the incorporated cellulose glycolic acid salts prevented could be. The formulations proposed so far to solve this problem must be as Technically too complex, the problem itself can be described as not being solved satisfactorily. So is z. B. according to the German interpretation 1152779 a combination of cellulose ether carboxylic acid salts and hydrogenated castor oil related to a To prevent phase separation. According to the German Auslegeschrift 1 156 927 a mixture of cellulose ether carboxylic acid salts and polyvinyl alcohol or polyvinyl pyrolidone and after German Auslegsschrift 1054 638 two different types of cellulose derivatives are the same Purpose used. Also the use of bentonite and urea for such cellulose ether carboxylic acids Cleaning agents containing salts have already been considered according to German Auslegeschrift 1152 779.

It has now been found that sedimentation-stable aqueous liquid detergents can be as described at the beginning mentioned type comes when it has a suspension-stabilizing content

a) 0.5 to 25 percent by weight, based on the total solids content, of a mixture of 40 to 60 percent by weight, based on the mixture, of capillary-active sulfobetaines and 60 to 40 percent by weight, based on the mixture, of C ₁₆ - to C ^ - Fatty alcohol sulfates and

b) at least 5, preferably 10 to 16 percent by weight, based on the total solids content, on capillary-active amine oxides and / or capillary-active ether sulfates

exhibit.

The capillary-active amine oxides are oxidation products of tertiary amines that have a higher alkyl radical containing 8 to 22, preferably 10 to 18 carbon atoms, with between the Nitrogen atom and the alkyl radical can also contain oxypropylene radicals. The two

Aqueous liquid detergents with a
Content of cellulose ether carboxylic acid salts

Patented for:

Henkel & Cie. GmbH.,
Düsseldorf-Holthaiisen, Henkelstr. 67

Named as the inventor

Dipl.-Chem. Dr. Western frieze,

Erkrath-Unterbach;

Dipl.-Chem; Dr. Rolf Puchta, Hilden (RhId.);

Dipl.-Chem. Dr. Wolfgang Gündel,

Düsseldorf-Oberkassel;

Dipl.-Chem. Dr. Horstmar Nagel,

Düsseldorf-Holthausen

other aliphatic ones located on the nitrogen atom Residues contain a maximum of 5, preferably 1 to carbon atoms.

As capillary-active ether sulfates are sulfation products of ethoxylated fatty alcohols or alkylphenol with 1 to 15, preferably 2 to 12, ethylene glycol residues in the molecule. The length of the. Alkyl or fatty alcohol residues in the ether sulfates can be the same as in the amine oxides. The amount of capillary active amine oxides or ether sulfates is preferably _{at least equal to the amount of C 16 -C M} fatty alcohol sulfates present.
The use of capillary-active sulfobetaines in detergents, cleaning agents, wetting agents and foaming agents is known per se, see German Auslegeschrift 606 and 1162 966. These capillary-active sulfobetaines are compounds of the general formula

R ₁

O - SO _a

^R a C- (CH ₈ ) _n

Rs R ₄

wherein Ft is a hydrophobic, i.e. straight or branched chain aliphatic or cycloaliphatic Represents a hydrocarbon radical with 8 to 20, preferably 12 to 18 carbon atoms, d <yr both ge

. 809 594/323

3 '■ 4'

saturated as well as unsaturated in nature, of fatty alcohols, such as those from the fatty acids of the

R ₁ and R _{2 are} aliphatic residues with a maximum of 5 carbon, coconut or palm kernel fat.

Substance atoms, R ₃ and R ₄ hydrogen atoms or ali- The liquid detergents according to the invention can

phatic hydrocarbon residues with at most also known hydrotropes, such as

3 carbon atoms and η one of the integers 1 5 lower alkyl and alkylarylsulfonates. These include

or 2 or capillary-active sulfobetaines, inter alia, the alkali metal sulfonates of benzene,

the likely formula of toluene, xylene, naphthalene, etc.

The active washing substances can be mixed with foam

Ri O SO ₈ stabilizers can be combined. These include

\, / '\ ίο, for example, higher molecular weight carboxylic acid or

^ ~ 7 ^ \ ./CH ₂ sulfonic acid amides, where the amide nitrogen is substituted

j ^ _ _ ated or unsubstituted. As a substituent

^2. ". ■ are primarily alkylol residues or polyglycol

¹ \ / \ · remains in question. In addition to the unsubstituted amides

R ₃ R ₁ H OH ₁₅ have the monoethanolamides and the reaction products of the unsubstituted amides with 1

wherein Ft is a hydrophobic, i.e. straight or up to 5 moles of ethylene oxide has proven useful. This

branched aliphatic or cycloaliphatic substances can be fatty acid amides, alkyl sulfon

Hydrocarbon radical with 8 to 20, preferably 12 acid amides or alkylbenzenesulfonic acid amides

represents to 18 carbon atoms, both of which originate ge ao.

both saturated and unsaturated in nature, liquid detergent concentrates are now

R ₁ and R _{2 are} aliphatic radicals with a maximum of 5 coals - preferably for working in washing machines.

material atoms, R ₃ and R ₄ hydrogen atoms or ali- provided, where a high foaming capacity or a

Phatic hydrocarbon residues with at most high foam resistance is undesirable. To this

3 mean carbon atoms. as to the liquid detergent according to the invention

These two interpretative publications deal mainly with achieving low-foaming ones

mainly detergent of powdery consistency; Add active washing substances or other substances,

Liquid detergents, which reduce the foaming power, are only mentioned in passing. It recommends

without focusing on the problem of suspension stabilization, therefore, combinations of different types of

tion is discussed in more detail. Therefore, the invention was to use 3 ° washing active substances that oppose each other

from these two explanatory documents not to interfere with the foam development. Such

to take. Combinations are, for example, soaps and syn-

The composition of the thetics according to the invention of the sulfate or sulfonate type, wherein the

Liquid detergent can also largely retain the foaming power of this combination of two

known products. 35 by adding non-ionic capillary active sub-

As washing active substances, the known substances can be reduced. If the washing anionic or non-ionic substances on a naturally active substance consist essentially of capillary-active licher or synthetic basis or their combination polyethylene glycol ethers, then an additional nation has to be used, which has a hydrophobic by water-soluble at room temperature addition residue, in particular an aliphatic hydrocarbon 40 products of propylene oxide to capillary-active polystyrene residue with 8 to 24, preferably 10 to 18 and ins- ethylene glycol ether as a foam press well proven,
particularly contain 10 to 16 carbon atoms. The anionic active detergents include, for example, soaps, alkylbenzene, advantageously in the form of their readily soluble salts, such as sulfonates, fatty alcohol sulfates, fatty acid monoglycerides, for example sodium, or easily soluble organic sulfates, fatty alcohol monoglycerol ether sulfates or other bases, such as. B. used in the form of salts of mono-, Didere sulfates of partial esters of higher fatty acids with or triethanolamine. Polyvalent alcohols, of course. In addition, fatty acids can also be used with one another as a mixture of esters or fatty alcohol ethers of oxyalkylsulfonic acids, for example sodium such as. B. fatty acid esters of oxypropane or dioxy salts in a mixture with the ethanolamine and or propanesulfonic acid, or of oxyalkylcarboxylic acids, 50 or potassium salts.

or fatty acid amides of aminosulphonic acids or The pyro- or tri-

of aminocarboxylic acids useful. Easily soluble salts of the polyphosphates can be added

according to the invention usable nonionic washing sodium, potassium or the amines, in particular the

active substances include especially the addition alkylolamines, which are clear

products from ethylene oxide to fatty alcohols, fatty solutions, slurries or pastes

acids or their partial ethers or partial esters with more than one can. If you put the washing alkalis, especially the

Valuable alcohols, ethylene oxide addition products, phosphates, in the form of their easily soluble potassium salts

to a higher molecular weight sulfonic acid or carboxylic acid, it must be taken into account that the potassium salts

amides, etc. Addition products of many organic washing active substances are also heavier

Ethylene oxide is soluble in higher molecular weight polypropylene glycols 60 than the sodium salts. Therefore, the

usable. Manufacture of concentrates in which the washing

Apart from alkalis and the washing active substances, the detergents according to the invention can be completely dissolved

those serving as suspension stabilizer components should be the concentrations of these preparations

C ₁₆ - to C ₂₄ -fatty alcohol sulfates also other fatty and the amounts of sodium and contained therein

alcohol sulfates with fewer than 16 carbon atoms 65 potassium ions adjust so that no undesirable

contain, preferably those with 10 to 14 and ins- Excretions of the less soluble salts instead of

contain 12 to 14 carbon atoms. Find your own here. Of course, all can be in the alkaline

. especially the sulphates of the C ₁₂ - to C _u fractions are present in the form of their concentrate

⁵ 6

Salts with readily soluble organic bases, such as applies, as described in the German Auslegeschrift 1162 966

Mono-, di- or triethanolamine are present. are described and how to implement them

The pyro-, tripoly- and higher polyphosphates of dimethyl fatty amines with epichlorohydrin and ankönnen wholly or partially by soluble organic final treatment of the thus formed, a chlorine chelating agent, such as B. niterilotriacetic acid or quaternary ammonium ethylenediamine tetraacetic acid containing 5 hydring groups Salts, to be replaced. salts with salts of sulphurous acid. This

The preparations according to the invention are thus before- Sulphobetaines are hereinafter referred to as »Oxysulpho-

preferably aqueous suspensions containing betaines ”. In both cases, the number becomes

30 to 60, preferably 40 to 50 percent by weight of the carbon atoms present in the fat residue dissolved or suspended substance, the dissolved to also being indicated; this fat residue came from natural

and suspended matter with the following composition lent fatty acids and was therefore straight-chain,
having:

a) Capillary-active amine oxides and / or capillary B e i s ρ i e 1 1

active ether sulfates (products containing ", ..." ......, · ,..,

¹ am capillary-active amine oxides have after ^1S Various Hussig detergents were used as follows

based on the currently available knowledge, the general composition is established:

greatest practical importance) in amounts of 8.0 percent by weight of alkyldimethylamine oxide

a total of 5 to 20, preferably 10 to 16 Ge. (Alkyl radical from C ₁₂ - to Qg coconut fatty acid),

percent by weight, but preferably at least 3.0 percent by weight of tallow fatty alcohol sulfate,

as much as C ₁₆ - to C ₂₄ fatty alcohol sulfate upstream ^ao 8.0 weight percent toluenesulfonate,

is available, 5.0 percent by weight water glass,

b) inorganic or organic complexing agents, 20.0 percent by weight potassium pyrophosphate,
such as pyro- and polyphosphates of the 0.6 percent by weight cellulose glycolic acid salt,
Alkalis or aminopolycarboxylic acid salts, the remainder sulfobetaine and water.

to 50, preferably 30 to 40 percent by weight, ^a5 ^. _, ... , .... . .....

c) Cellulose ether carboxylic acid salts, especially eel-, ^The liquid detergent samples contained 1 to 5, preferably the following amounts of sulfobetaine based on the 1 to 2 percent by weight, total weight of the liquid detergent:

d) Mixture of 40 to 60 percent by weight, based on 3.0 percent by weight of C ₁₂ sulfobetaine,
on the mixture of capillary-active sulfobetaines ³ ° 3.6 percent by weight of Cj ₈ -sulfobetaine,
and 60 to 40 percent by weight, based on the 3.2 percent by weight of C ^ sulfobetaine,
Mixture of C ₁₆ to C ₂₄ fatty alcohol sulfates, 3.1 percent by weight Cuj-oxysulfobetaine,
0.5 to 25, preferably 6 to 22 percent by weight, 3.7 percent by weight of C ₁₂ oxysulfobetaine,

e) other common ingredients of liquid washing - _{3.3 percent by weight C 14 oxysulfobetaine,}
agents (water glass, solubilizers, such as ³⁵ 3.9 percent by weight of C ₁₄ -oxysulfobetaine,
Toluenesulfonate, xylene sulfonate, etc.), 0 to 40, 3.8 percent by weight of C ₁₈ oxysulfobetaine.
preferably 20 to 30 percent by weight, and ^. . ". . ; _. . .... ..... "". "

if necessary, ^{the detergents} were milky-white, easily pourable

f) Anionic organic washing active substance, ins- ^ suspensions in which after 3 weeks special washing active sulphates and / or ⁴ ° storage time no segregation into sulphonates with the exception of those mentioned under a) could be recognized.

0 to 30, preferably 15 to 25 percent by weight. Appropriately composed liquid detergents

^e without sulfobetaine showed a significantly lower rate

As a solvent for the dissolved and suspended suspension stability; the cellulose glycolate salts

Substances are preferably water; it may in part 45 had settled in general after 3 weeks,

by water-soluble organic solvents, how similarly behaved, products in which the TaIg-

z. B. lower alcohols or ether alcohols with 1 to fatty alcohol sulfate by the appropriate amount of

4 carbon atoms replaced, with the portion of coconut fatty alcohol sulfate having been replaced.
mostly of water-soluble organic solvents

is not greater than 20%> preferably not more than 50 Example 2

10 ° / o 'and in particular 1 to 8 ° / o of the weight of the *

Can be solvent. The recipe of the one described in this example

Liquid detergent differed from that of the two

Examples game 1 by a lower content of amine oxide

55 and a higher content of tallow fatty alcohol sulfate;

For the production of the washing machines described here, both were in an amount of 5.5 percent by weight

Medium samples were the ingredients of the detergent before. The following sulfobetaine

means mixed in the specified amount, with amounts based on the total weight of the liquid

Water added and worked into the water bath, detergent, for so long:

heated until everything was resolved. Then the cellu- 60 3 _{? Percentage by weight} Q ₄ -Sulf obetain,

Loseglykolsauren salts in the solution obtained with _{5 9} percent by weight of C ₁₄ sulfobetaine.
Dispersed with the help of a high-pitched agitator.

As sulfobetaines, there were no reaction products here either after standing for 3 weeks Dimethyl fatty amines used with propane sultone to identify signs of sedimentation; would they omitted sulfobetaine or tallow fatty alcohol-1135 in the German Auslegeschrift 65 mentioned at the beginning 606 are described. In sulphate, these products are referred to as »sulphobetaines« due to the corresponding amount of coconut fat. In addition, alcohol sulphate was replaced so the celiosis had been removed Sulphobetaines containing oxy groups, glycated salts, are deposited after a short time.

Claims (1)

Patent claims: 1. Aqueous liquid detergents containing cellulose ether carboxylic acid salts based on conventional, detergent constituents that are inherently solid, marked by a suspension stabilizing Content of a) 0.5 to 25 percent by weight, based on the total solids content, of a mixture of 40 to 60 percent by weight, based on the mixture, of capillary-active sulfobetains and 60 to 40 percent by weight, based on the mixture, of C ₁₈ to C ₂₄ -Fatty alcohol sulfates and ' b) at least 5 percent by weight, based on the total solids content, at capillary. active amine oxides and / or capillary-active Ether sulfates. 2. Liquid detergent according to claim 1, characterized as follows characterized in that the amount of the mixture of capillary-active sulfobetaines and C ₁₆ - to C _a4 fatty alcohol sulfates is 6 to 22 percent by weight of the solids content present in the liquid detergent. - s $ 3. Liquid detergent according to claim 1 and 2, characterized in that the content of capillary-active amine oxides and / or capillary-active ether sulfates is 10 to 16 percent by weight. based on the total solids content. 4. liquid washing agent according to claim 1 to 3, characterized gdosa that the as a solvent serve '»ίο water partly through water-soluble organic solvent is replaced. . 5. Liquid detergent according to claim 1 to 4, characterized in that the water-soluble organic solvents are present in an amount of at most 20%, preferably at most 10 ° / ₀ , and in particular 1 to 8%, based on the weight of the mixture of water and solvents. 6. Liquid detergent according to claim 1 to 5, characterized in that as water-soluble organic solvents, lower alcohols or ether alcohols with 1 to 4 carbon atoms are present. 7. Liquid detergent according to claim 1 to 6, characterized in that it is active as a capillary Sulfobetaines contain compounds of the general formula R ₁ R ₂ O - SO, /
CH ₂ - (CHg) n ^CHs 55 wherein Ft is a hydrophobic, ie straight or branched-chain aliphatic or cycloaliphatic hydrocarbon radical having 8 to 20, preferably 12 to 18 carbon atoms, Ri O \ CHo ^Ft 7 ^N / , -CH which can be both saturated and unsaturated in nature, R ₁ and R _{2 are} aliphatic ^ radicals with a maximum of 5 carbon atoms and η is one of the integers 1 or 2. 8. Liquid detergent according to claim 1 to 6, characterized in that it is active as capillary Sulfobetaines contain compounds of the likely formula , CHo OH wherein Ft is a hydrophobic, ie straight or branched-chain aliphatic or cycloaliphatic hydrocarbon radical having 8 to 20, preferably up to 18 carbon atoms, which can be of a saturated or unsaturated nature, and R ₁ and R _{2 are} aliphatic radicals with at most carbon atoms. 9. Liquid detergent according to claim 1 to 6, characterized in that the solids are as follows Composition: a) capillary-active amine oxides and / or capillary-active ether sulfates in total amounts of 5 to 20, preferably 10 to 16 percent by weight, but preferably at least as much as C ₁₆ to C ₂₄ fatty alcohol sulfate is present, b) inorganic or organic complexing agents such as pyro- and polyphosphates the alkalis or aminopolycarboxylic acid salts, 20 to 50, preferably 30 to 40 percent by weight, c) celMose ether carboxylic acid salts, in particular cellulose glycolic acid salts, 1 to "5, preferably 1 to 2 percent by weight, d) Mixture of 40 to 60 percent by weight, based on the mixture, of capillary-active sulfobetaines and 60 to 40 percent by weight, based on the mixture, of C ₁₆ to C ₂₄ fatty alcohol sulfates, 0.5 to 25, preferably 6 to 22 percent by weight, e) other common ingredients of liquid detergents (water glass, solvents, such as z. B. toluenesulfonate, xylene sulfonate, etc.), 0 to 40, preferably 20 to 30 percent by weight, and if necessary f) Anionic, organic washing active substance, in particular washing active sulfates and / or sulfonates with the exception of those mentioned under a), 0 to 30, preferably 15 to 25 percent by weight. Considered publications: German interpretative document No. 1135 606. 709.710 / 575 12.67 Q Bundesdruckerei Berlin