US3629126A

US3629126A - Liquid detergent composition

Info

Publication number: US3629126A
Application number: US867965A
Authority: US
Inventors: Walter Fries; Rolf Nagel Puchta; Wolfgang Gundel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1965-03-30
Filing date: 1969-10-20
Publication date: 1971-12-21
Anticipated expiration: 1988-12-21
Also published as: DE1257339B; DK126126B; NL6602717A; CH473218A; AT270027B; BE678536A; SE342254B; GB1077646A; ES324866A1

Abstract

LIQUID DETERGENT COMPOSITIONS COMPRISING 40 TO 70% WATER AND 30 TO 60% DISSOLVED AND SUSPENDED MATERIALS CONSISTING ESSENTIALLY OF THE FOLLOWING IN PERCENT BY WEIGHT BASED UPON THE TOTAL WEIGHT OF THE SUSPENDED AND DISSOLVED MATERIAL: 1 TO 5% OF AT LEAST ONE SALT OF A CELLULOSE ETHER CARBOXYLIC ACID, 5 TO 20% OF AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF SURFACE ACTIVE AMINE OXIDES AND SURFACE ACTIVE ETHER SULFATES, 0 TO 40% CONVENSTANCES OTHER THAN THE AMINE OXIDES AND/OR ETHER SULFATES AND 0.5 TO 25% OF A MIXTURE OF 40 TO 60% OF AT LEAST ONE C16 TO C24 FATTY ALCOHOL SULFATE AND 60 TO 40% OF AT LEAST ONE SULFOBETAINE.

Description

United States Patent US. Cl. 252-526 6 Claims ABSTRACT OF THE DISCLOSURE Liquid detergent compositions comprising 40 to 70% water and 30 to 60% dissolved and suspended materials consisting essentially of the following in percent by weight based upon the total weight of the suspended and dissolved material: 1 to of at least one salt of a cellulose ether carboxylic acid, 5 to 20% of at least one member selected from the grou consisting of surface active amine oxides and surface active ether sulfates, O to 40% conventional detergent additives, 0 to 30% of wash active substances other than the amine oxides and/or ether sulfates and 0.5 to 25% of a mixture of 40 to 60% of at least one C to C fatty alcohol sulfate and 60 to 40% of at least one sulfobetaine.

This application is a continuation of Ser. No. 535,660, filed Mar. 17, 1966.

This invention relates to liquid laundry detergents. It more particularly refers to such liquid detergents which contain suspended but undissolved therein substances which render the detergent composition suitable for use as a boiling water detergent.

It is known to produce warm or cool water detergent compositions in liquid form suitable for use with delicate fabrics such as stockings, lingerie, etc. As can be appreciated, it would be desirable to produce detergent compositions of a somewhat similar nature, in the liquid form, which were suitable for use in more ordinary laundry applications which operate at much higher temperatures, i.e. approaching the boiling point of water.

It has previously been found that the inclusion of suspended cellulose ether carboxylic acid salts, particularly cellulose glycolic acid salts, renders liquid detergent compositions suitable for more general laundry application at the higher temperatures. One particular problem which has faced the art in this situation has been the tendency or inclination of the cellulose glycolic acid salts to deposit out of the suspension. This problem has been attacked previously but has as yet not been the subject of a truly satisfactory solution.

Some of the attempted solutions to this problem include: combination of cellulose ether carboxylic acid salts and hydrogenated castor oil (see German Pat. 1,152,779); cellulose ether carboxylic acid salts and polyvinyl alcohol of polyvinyl pyrrolidone (see German Pat. 1,156,927); two different types of cellulose derivatives (see German Pat. 1,064,638); and combinations of cellulose ether carboxylic acid salts with bentonite and/or urea combined with the cleansing agents (see German Pat. 1,152,779).

As can be appreciated, none of the aforementioned, or any other, proposed solution has been wholly acceptable to the art nor have these proven to be a proper and adequate technical solution of the problem.

It is therefore an object of this invention to provide a satisfactory liquid detergent composition which is usable for general purpose washing.

It is another object of this invention to provide a liquid detergent composition containing suspended cellulose ether carboxylic acid salt which is stable at about the boiling point of water.

It is a further object of this invention to provide a novel means of maintaining a cellulose ether carboxylic acid salt in aqueous suspension at about the boiling point of water.

It is still another object of this invention to provide a new liquid detergent composition.

It is a still further object of this invention to provide a novel sedimentation stabilizer system.

Other and additional objects of this invention will be apparent from a full consideration of this entire specification including the claims appended hereto.

In accordance with and fulfilling these objects, one embodiment of this invention resides in the discovery that aqueous suspensions of cellulose ether carboxylic acid salt, particularly cellulose glycolic acid salt, have markedly improved sedimentation stability if there is present in the suspension system a mixture of at least one sulfobetaine and at least one C to C fatty alcohol sulfate.

The sulfobetaine portion of this mixture comprises at least one compound of at least one of the formulas:

(1) R1 O SO wherein Ft is a hydrophobic moiety substituent, suitably 0f the straight or branched chain aliphatic or cycloaliphatic hydrocarbon type having about 8 to 24 carbon atoms, preferably containing about 12 to 18 carbon atoms; R and R are the same or different and are aliphatic residues containing up to about 5 carbon atoms; R and R are the same or different and may be hydrogen or aliphatic hydrocarbon residues containing up to about 3 carbon atoms; and n is the integer one (1) or two (2).

As previously noted, this phenomenon has great utility and applicability in the general purpose liquid laundry detergent art.

A typical liquid detergent composition contains various components to perform various given functions including: anionic surfactants and/or non-ionic surfactants; fatty alcohol sulfate other than the suspension stabilizer referred to above; hydrotropic substances; foam stabilizers; washactive substances such as soaps; and wash alkalis. All these components of liquid detergent compositions are known per se and are known for use in this art. Detergent additives such as water glass, bleach stabilizer, optical brighteners, organic dirt dispersants and perfumes can also be included.

The anionic surfactants are exemplified by soaps, alkylbenzene sulfonates, fatty alcohol sulfates, fatty acid monoglyceride sulfates, fatty alcohol monoglycerin ether sulfates, other sulfates of partial esters of higher fatty acids with polyhydric alcohols, fatty acid or fatty alcohol esters of oxalkyl sulfonic acids, e.g. fatty acid esters of hydroxy and dihydroxy propane sulfonic acid or of oxalkyl carboxylic acids, and/or fatty amides of amino sulfonic acids or amino carboxylic acids. They also include amine oxides which are oxidation products of tertiary amines. These tertiary amines have a higher alkyl radical containing about 8 to 22 (preferably 18) carbon atoms and two lower aliphatic radicals containing up to about 5 (preferably 13) carbon atoms. Optionally, the higher alkyl radical can be linked to the amine nitrogen through one or more hydroxy propyl groups. The surfactant ether sulfates are sulfation products of ethoxylated fatty alcohols or alkyl phenols having about 1 to (preferably about 2 to 12) ethylene glycol moieties per molecule. The alkyl groups of the alkyl phenol and the fatty alcohol suitably contain about 8 to 22 (preferably 10 to 18) carbon atoms.

The non-ionic surfactants are exemplified by addition products of ethylene oxide to fatty alcohols, fatty acids or partial esterification or etherification products thereof with polyhydric alcohols; addition products of ethylene oxide to high molecular weight sulfonic and/or carboxylic acids or acid amides; and addition products of ethylene oxide to higher molecular weight polypropylene glycol.

The anionic surfactant may be combined with the nonionic surfactant where the combination has an hydrophobic radical such as an aliphatic hydrocarbon radical having about 8 to 24 carbon atoms, preferably 10 to 16 carbon atoms.

The additional fatty alcohol sulfate generally contains less than about 16 carbon atoms, preferably 10 to 14 carbon atoms, and most preferably 12 to 14 carbon atoms such as fatty alcohols prepared from coconut or palmkernel oil fatty acids.

The hydrotropic substances referred to above are exemplified by alkali sulfonates of aromatic hydrocarbon residues including benzene, toluene, xylene, naphthalene and other similar residues.

Various foam stabilizers can be used including higher molecular weight carboxylic or sulfonic acid amides substituted or unsubstituted on the amide nitrogen. Examples of such amides include fatty acid amides, alkyl sulfonic acid amides or alkylbenzene sulfonic acid amides. Where the amide nitrogen is substituted, such substituent may be derived from monoethanol amine or like substances or the substituent may be a mono or polyalkylol or polyglycol residue. Further, the reaction products of the above substituted or unsubstituted acid amides with about 1 or 5 moles of ethylene oxide have been found to be suitable for this application.

The wash-active substances include soaps, synthetic detergents of the sulfate or sulfonate type and surface active polyethylene glycol ethers. It has been found desirable to utilize combinations of wash-active substances in order to invoke the foam suppressing properties of each with respect to the other whereby the total foaming propensity of the composite wash-active component is substantially reduced. Where required or desired, additional foam suppressors, such as for example addition products of propylene oxide to surface active polyethylene glycol ethers which are water-soluble at room temperature, may be used.

Anionic wash-active substances are preferably used in the form of a readily water-soluble salt or organic base. These include sodium or potassium as the most common examples of salts and mono-, dior trialkanol (particularly ethanol) amine as the most common examples of useful organic bases. Of course, mixtures of salts and/or bases can be used.

Wash alkalis generally include pyroor tripolyphosphates in the form of readily water-soluble salts or organic bases of the same character as described above. Also included in this group of components are chelating agents such as for example nitrilo-triacetic acid or ethylene diamine tetra-acetic acid in their salt or other soluble form.

Other conventional liquid detergent components which can be employed in compositions of this invention include water-glass and solubilizers such as toluene sulfonate, xylene sulfonate, etc.

It will be appreciated that the preferred medium for the compositions of this invention is water. It has been found to be practical however to, in some cases, replace a part of the water with any of a number of water-soluble organic solvents such as for example lower alkanols having about 1 to 4 carbon atoms.

Suitably, compositions according to this invention are made up of about 40 to 70 percent by Weight, preferably to percent, of the solvent medium, water or water containing up to about 20 percent by weight of a soluble cosolvent as referred to above. It is preferred to use at most about 10 percent and most preferred to use 1 to 8 percent of the cosolvent.

The remainder of the liquid detergent composition, 30 to 60 percent by Weight and preferably 40 to 50 percent is made up of the dissolved and suspended matter. This portion of the liquid detergent composition includes the above recited components in the following proportions by weight based upon the total weight of suspended or dissolved matter:

Amine oxide or surfactant ether sulfate or combinations of both, about 5 to 20 (preferably 10 to 16) percent, most preferably at least as much as the fatty alcohol sulfate as hereinafter stated:

lPyroand tripolyphosphates as well as related materials alone or in combination with each other, about 20 to 50 (preferably 30 to 40) percent;

Cellulose ether carboxylic acid salt, about 1 to 5 (preferably 1 to 2) percent:

Mixture of sulfobetaine and C and C fatty alcohol sulfate, about 0.5 to 25 (preferably 6 to 22) percent. Each component of this mixture comprises about 40 to 60 percent of the mixture;

Other conventional liquid detergent components as referred to hereinbefore, about 0 to 40 (preferably 20 to 30) percent; and

Other wash-active substances than those referred to hereinbefore as amine oxides or surfactant ether sulfates, such as for example wash-active sulfates or sulfonates, about 0 to 30 (preferably 15 to 25) percent.

The following examples are set forth as illustrative of the instant invention and should in no way be construed as limiting on the scope thereof.

EXAMPLES For the preparation of the detergents described here the components of the detergent were mixed in the quantity indicated, whereupon water was added and then heated on a Water bath until everything had dissolved. Thereupon, the cellulose glycolic acid salts were dispersed in the resultant solution by means of a high speed agitator.

As sulfobetaines there were used reaction products of dimethyl fatty amines with propanesultone, such as described in the aforementioned German provisional patent 1,135,606. These products are referred to below as sulfobetaines. There were also used sulfobetaines containing hydroxy groups, such as described in German provisional patent 1,162,966 and as obtained by reaction of dimethyl fatty amines with epichlorhydrin followed by treatment of the resultant quaternary ammonium salts containing a chlorhydrin group, with salts of sulfurous acid. These sulfobetaines are hereinafter referred to as hydroxy sulfobetaines. In both cases, the number of carbon atoms present in the fatty radical is also indicated; this fatty radical came from natural fatty acids and was, therefore, a straight-chain radical.

EXAMPLE 1 Various liquid detergents of the following general composition were prepared:

8.0 percent by weight alkyl dimethylamine oxide (alkyl radical from C to C (coconut oil acid) 3.0 percent by weight tallow oil alcohol sulfate 8.0 percent by weight toluene sulfonate 5.0 percent by weight waterglass 20.0 percent by weight potassium pyrophosphale 0.6 percent by weight cellulose glycolic acid salt Balancesulfobetaine and water The liquid detergent samples contained in detail the following quantities of sulfobetaine, referred to the total Weight of the liquid detergent:

(1a) 3.0 percent by weight C sulfobetaine (lb) 3 .6 percent by weight C sulfobetaine 3.2 percent by weight C sulfobetaine ld) 3.1 percent by weight C hydroxysulfobetaine (1e) 3.7 percent by weight C hydroxysulfobetaine (1f) 3.3 percent by weight C hydroxysulfobetaine (1g) 3.9 percent by weight C hydroxysulfobetaine (1h) 3.8 percent by weight C hydroxysulfobetaine lj) The detergents were milky White, readily pourable suspensions in which no signs of separation could be noted even at the end of 3 weeks of storage.

Liquid detergents of corresponding composition without sulfobetaines showed a substantially poor stability of the suspensions; cellulose glycolic acid salts in general deposited within 3 weeks. Products in which the tallow oil alcohol sulfate had been replaced by the corresponding quantity of coconut oil alcohol sulfate behaved in similar manner.

EXAMPLE 2 The formula of the liquid detergents described in this example differed from that of Example 1 by a smaller content of amine oxide and a higher content of tallow oil alcohol sulfate; both were present in an amount of 5.5 percent by Weight of the detergent. The following amounts of sulfobetaine, referred to the total weight of the liquid detergent were incorporated:

(2a) 3.7 percent by weight C sulfobetaine (2b) 5.9 percent by weight C sulfobetaine (2c) In this case also no signs of sedimentation could be noted after standing for 3 weeks; if the sulfobetaine was omitted or the tallow oil alcohol sulfate replaced by the corresponding amount of coconut oil alcohol sulfate,

the cellulose gycolic acid salts deposited after only a short time.

What is claimed is:

1. A liquid detergent composition consisting essentially of 40 to 70% water and 30 to 60% dissolved and suspended components as follows in percent by weight based on the total weight of the dissolved and suspended components:

5 to 20% of at least one member selected from the group consisting of surface active amine oxides having an 8 to 22 carbon atom alkyl group and two alkyl radicals containing up to about 5 carbon atoms and surfactant ether sulfates containing about 1 to ethylene glycol groups per molecule,

to 50% of a member selected from the group consisting of water soluble sodium, potassium and alkanol amine, pyroand tri-polyphosphates,

1 to 5% of cellulose glycolate, and

0.5 to of a mixture consisting of 40 to 60% of at least one C to C fatty alcohol sulfate and 60 to 40% of at least one sulfobetaine selected from the group consisting of wherein Ft is a hydrophobic radical selected from the group consisting of alkyl and cycloalkyl containing 8 to 24 carbon atoms, R and R is each an alkyl containing up to 5 carbon atoms, R and R is each a member selected from the group consisting of hydrogen and alkyl containing up to 3 carbon atoms and n is a whole positive integer of at most 2.

2. A composition according to claim 1, additionally containing at least one water soluble lower alkanol.

3. A composition according to claim 1, wherein said dissolved and suspended components comprise in percent by Weight based upon the total weight of the dissolved and suspended components the following:

10 to 16% of at least one member selected from the group consisting of said amine oxides and said ether sulfates,

1 to 2% of cellulose glycolate and 6 to 22% of said mixture of sulfobetaine and fatty alcohol sulfate.

4. A composition according to claim 1, wherein said amine oxide and said ether sulfate together are present in an amount at least equivalent to the amount of said fatty alcohol sulfate.

5. A composition according to claim 1, consisting essentially of:

8.0 percent by weight of alkyl dimethylamine oxide wherein said alkyl group is derived from (I -C coconut oil acid,

3.0 percent by weight tallow oil alcohol sulfate,

8.0 percent by weight toluene sulfonate,

5.0 percent by weight water glass,

20.0 percent by weight potassium pyrophosphate,

0.6 percent by weight cellulose glycolate,

3.0-4.0 percent by weight sulfobetaine,

balancewater.

6. A composition according to claim 1, consisting essentially of:

5 .5 percent by weight of alkyl dimethylamine oxide, the

alkyl group of which is derived from C to C coconut oil acid, 5.5 percent tallow oil alcohol sulfate,

8.0 percent by weight toluene sulfonate,

5.0 percent by weight water glass,

20.0 percent by weight potassium pyrophosphate,

0.6 percent by weight cellulose glycolate,

3.7-5.9 percent by weight sulfobetaine, and

balancewater.

References Cited UNITED STATES PATENTS 2,202,741 5/1940 Maxwell 252161 LEON D. ROSDOL, Primary Examiner M. HALPERN, Assistant Examiner U.S. 'Cl. X.R. 252-545