US3862965A

US3862965A - Shaped washing agents based on synthetic tensides

Info

Publication number: US3862965A
Application number: US306014A
Authority: US
Inventors: Lothar Werner; Werner Schneider
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1969-10-01
Filing date: 1972-11-13
Publication date: 1975-01-28
Anticipated expiration: 1992-01-28
Also published as: DE1949562A1; NL7013063A; AT301726B; FR2064076B1; BE756790A; NL164602C; DE1949562B2; FR2064076A1; DE1949562C3

Abstract

Shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from 50% to 85% by weight of a tenside mixture consisting essentially of (1) from 70% to 100% by weight of the tenside mixture of a sulfonate mixture consisting essentially of (a) from 10% to 80% by weight of the sulfonate mixture of a water-soluble salt of a monoester of a sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with aliphatic alcohols having 8 to 18 carbon atoms and (b) from 20% to 90% by weight of the sulfonate mixture of a water-soluble salt of an olefin sulfonate having 10 to 18 carbon atoms, and (2) from 0 to 30% by weight of the tenside mixture of other tensides selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, (B) from 12% to 47% by weight of non-tenside waterinsoluble builders customarily utilized in shaped washing agents, and (C) from 3% to 15% by weight of water.

Description

United States Patent 11 1 Werner et a1.

1451 Jan. 28, 1975 1 SHAPED WASHING AGENTS BASED ON SYNTHETIC TENSIDES [73] Assignee: Henkel and Cie GmbH,

Dusseldorf-Holthausen, Germany 22 Filed: Nov. 13, 1972 211 Appl. No.: 306,014

Related U.S. Application Data [63] Continuation of Ser. No. 76,203, Sept. 28, 1970,

abandoned.

[] Foreign Application Priority Data Oct. 1, 1969 Germany 1949562 [52] U.S. Cl. 252/555, 252/557 [51] Int. Cl ..Cl1d 3/066 [58] Field of Search 252/121, 535, 538, 555, 252/557 [5 6] References Cited UNITED STATES PATENTS 3,224,976 12/1965 Farrar 252/119 3,247,121 4/1966 Hendricks... 252/117 3,312,627 4/1967 Hooker 252/152 3,523,089 8/1970 Garrett 252/161 3,629,127 12/1971 Palmer et a1. 252/538 X 3,640,882 2/1972 Groves 252/121 3,705,114 12/1972 Sweeney et a1. 252/555 FOREIGN PATENTS OR APPLICATIONS 798,803 11/1968 Canada 252/557 Primary E.ramt'nerStephen .1. Lechert, Jr. Attorney, Agent, or Firm--Hammond & Littell [57] ABSTRACT Shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from to 85% by weight of a tenside mixture consisting essentially of 1) from to 100% by weight of the tenside mixture of a sulfonate mixture consisting essentially of (a) from 10% to by weight of the sulfonate mixture of a water-soluble salt of a monoester of a sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with aliphatic alcohols having 8 to 18 carbon atoms and (b) from 20% to by weight of the sulfonate mixture of a water-soluble salt of an olefin sulfonate having 10 to 18 carbon atoms, and (2) from O to 30% by weight of the tenside mixture of other tensides selected from the group consisting of anionic surface-active compounds, non-ionic surfaceactive compounds and amphoteric surface-active compounds, (B) from 12% to 47% by weight of nontenside water-insoluble builders customarily utilized in shaped washing agents, and (C) from 3% to 15% by weight of water.

7 Claims, No Drawings SHAPED WASHING AGENTS BASED ON SYNTHETIC TENSIDES This is a continuation of Ser. No. 76,203, filed Sept. 28, 1970, now abandoned.

THE PRIOR ART Since the emergence of synthetic tensides, soap has more and more been replaced by the synthetic tensides, above all in the production of powdered detergents. There has been no lack of attempts to use the synthetic tensides, particularly of the sulfate or sulfonate type, also for the production of piece-shaped washing agents, and there are a great number of respective proposals in the literature. In spite of this, on the market, washing agent pieces based on synthetic tensides play only a small role compared to washing agent pieces based on soap. There are substantially two reasons for this. The first reason is in the different physical properties and the second in the different physiological properties of soap, on the one hand, and synthetic tensides, particularly those of the sulfate and sulfonate type, on the other hand.

Cakes of soap have the ability to absorb large amounts of water in contact with it, and, thereby, first form a still solid gel. If one washes with such a soap, swollen on a part of the surface, the soap substance rubs off quicker at the swollen areas than at the nonswollen ones, so that the desired foam formation occurs quicker than usual. No loss of soap occurs in this. Washing agent cakes based on the named synthetic tensides behave completely differently. In them the area in which the swollen material adheres solidly to the residual piece is much smaller. In most cases, on the surface of the pieces a smeary mass is formed, which rubs off immediately in washing with such a cake and produces a much higher tenside concentration than would be required for the desired foam formation. For this reason greater material losses occur.

But also in drying of the partly swollen cakes a remarkable difference appears. The classical soap cakes lose their moisture with a reversal of the swelling and a close union between the non-swollen material and the initially swollen surface is maintained. In cakes from synthetic tensides, the mechanical union between the two parts is so far broken that also in drying of the surface the initially solid structure of the cake is no longer maintained.

A further disadvantage of the known washing agent cakes based on synthetic tensides lies in the strong degreasing of the skin. After washing with them, the disagreeable sensation of a dried-out skin remains.

The mechanical and physiological properties of washing agent cakes based on synthetic tensides can indeed be improved by incorporation of waterinsoluble soap cake builders, but even these improved cakes do not satisfy the requirements for a satisfactory washing agent cake.

OBJECTS OF THE INVENTION An object of the present invention is the development of a shaped washing agent composition based on synthetic tensides which overcomes the drawbacks mentioned above and can be utilized in place of hand soap cakes.

Another object of the invention is the development of shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from 50 percent to 85 percent by weight of a tenside mixture consisting essentially of (1) from to 100% by weight of the tenside mixture of a sulfonate mixture consisting essentially of (a) from 10% to by weight of the sulfonate mixture of a water-soluble salt of a monoester ofa sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with aliphatic alcohols having 8 to 18 carbon atoms and (b) from 20% to 90% by weight of the sulfonate mixture ofa water-soluble salt of an olefin sulfonate having 10 to 18 carbon atoms, and (2) from 0 to 30% by weight of the tenside mixture of the other tensides selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, (B) from 12% to 47% by weight of non-tenside waterinsoluble builders customarily utilized in shaped washing agents, and (C) from 3% to 15% by weight of water. These and other objects of the invention will become more apparent as the description therof proceeds.

DESCRIPTION OF THE INVENTION The invention relates to shaped washing agents based on synthetic tensides, which do not have the above described disadvantages. The shaped washing agents of the invention are characterized by the following composition:

50% to preferably 55% to 80% by weight of a tenside mixture composed of:

70% to 100% preferably 80% to 95% by weight of a sulfonate mixture of:

10% to 80% preferably 20% to 70% by weight of a water-soluble salt of a monoester of a sulfodicarboxylic acid, containing 3 to 8 carbon atoms, with aliphatic alcohols having 10 to 18 carbon atoms,

20% to preferably 30% to 80% by weight of a water-soluble salt of an olefin sulfonate with 10 to 18 carbon atoms in the molecule,

0 to 30% by weight of other tensides;

at least 12%, preferably at least 15% by weight of other non-tenside-like water-insoluble builders which, in themselves, are customary in shaped washing agents; and

3% to 15%, preferably 5% to 10% by weight of water.

The other tensides, optionally present in the tenside mixture, can be anionic, amphoteric, or nonionic. The shaped washing agents of the invention, in addition to containing ingredients customary in such products, such as superfatting agents, can contain impurities, originating from the tensides, etc. llnsofar as the below more extensively described water-insoluble superfatting agents (particularly fatty acids and fatty alcohols) are present as solids at temperatures of 30C, and preferably of 40C, they act as builders and belong to the other customary builder materials in the frame of the above recipe.

The above-defined surface-active sulfodicarboxylic acid monoesters are known and are accessible by various ways. Monoesters of aliphatic sulfodicarboxylic acids with 4 to 8 carbon atoms, such as sulfoalkanedioic acids having 4 to 8 carbon atoms, such as sulfoalkanedioic acids having 4 to 8 carbon atoms, are, for example, obtained by bisulfite addition to the corresponding monoesters of unsaturated dicarboxylic acids. sulfodicarboxylic acid monoesters can, however, be

also prepared by the introduction of the sulfonate group into the dicarboxylic acid radicaland subsequent conversion of the sulfodicarboxylic acid or its salts to the monoester. Thus, the monoester of the sulfophthalic acid is obtained by treating of phthalic acid monoesters with saturated alcohols with appropriate sulfonating agents. For this preparation of the shaped detergents, according to the invention, the monoesters of sulfosuccinic acid are preferentially used.

The alcohol radicals present in the named compounds are derived from preferably saturated, straightchain, primary aliphatic alcohols such as alkanols with to 18, preferably 12 to 14 carbon atoms. The alcohols can be of synthetic origin or be formed by reduction of synthetic or natural fatty acids. Preferably, the alcohol mixture obtained from coconut or palm kernel fatty acids, and particularly lauryl alcohol or the mixture oflauryl and myristyl alcohol separated from these fatty alcohol mixtures, are used. Such mixtures can contain fatty alcohols with more than 18 and less than 10, preferably those with 8 carbon atoms, however at least 50, and preferably 70% of the fatty alcohols or fatty alcohol radicals should contain 10 to 16, and particularly 12 to 14, carbon atoms.

Of particular practical importance are sulfosuccinic acid monoesters of fatty alcohols derived from coconut or palm kernel fatty acids or the respective C 2 to C fractions.

The olefin sulfonates utilized in the shaped washing agents of the invention are accessible by sulfonation of straight or branched-chain olefins having a terminal or non-terminal double bond by known procedures. For the shaped washing agents, according to the invention, preferably products are used which consist preponderantly of at least 70%, and preferably to more than 85%, of straight-chain olefin sulfonates and of these the sulfonates from straight-chain a-olefins are preferred.

Various processes for the preparation of olefin sulfonates are known. Of particular practical importance is a procedure in which the olefins are first reacted with gaseous sulfur trioxide in the presence of inert gases. 1 to 2, preferably 1 to 1.5 mols of S0 are used per mol of olefin. An intermediate is formed which gives, after acidic or alkaline hydrolysis at elevated temperatures, the desired sulfonate.

The thus obtained sulfonates are chemically nonhomogenous. They consist essentially of a mixture of hydroxyalkane sulfonates, alkene sulfonates and disulfonates. The latter can also possess hydroxyl groups. All the named substances, in regard to the position of the sulfonate group or groups, the hydroxyl group, and the double bond, can be present as mixtures of isomers. The quantitative ratio of hydroxyalkane sulfonates, alkene sulfonates and disulfonates depends to a certain extent upon the conditions of sulfonation and hydrolysis. Above all, the working conditions during hydrolysis influence the quantitative proportion of hydroxyalkane sulfonates and alkene sulfonates. With an increasing excess of sodium hydroxide solution in the hydrolysis and with rising hydrolysis temperature (50 to 200C, preferably 90 to 160C) the amount of hydroxyalkane sulfonates is reduced in favor/of the alkene sulfonates.

Both the sulfodicarboxylic acid monoesters and the olefin sulfonates are obtained, depending upon the selected preparation procedure, in a more or less colored state. Above all, the products obtained by sulfonation with gaseous sulfur trioxide are sometimes colored yellowish or brownish, and it may be desirable to bleach these sulfonates. For bleaching, oxidizing bleaching agents such 5.20; o so iu hypgchlorite, are usable- With the use of sodium hypochlorite, slight amounts of sodium chloride remain in the sulfonation product. In addition, the sulfonates contain often slight amounts of sodium sulfate. The amount of these neutral salts should, however, be not greater than 15 percent and preferably notgreater than 15 percent with reference to the anhydrous tenside. In many cases, the amount of neutral salts is much less and is for instance 1% to 5%.

The favorable properties of the washing agent cakes, according to the invention, are still preserved if limited amounts, up to 30% by weight of the tensides, of other tensides are also present. These tensides can be anionic, nonionic or amphoteric. Most of them contain a preferably straight-chain alkyl radical of 8 to 18, preferably 12 to 16 carbon atoms.

Within the scope of the anionic tensides, the sulfonates and the sulfates are of particular practical importance. To them belong, for example, the alkylbenzene sulfonates, fatty alcohol sulfates, sulfated adducts of 0.5 to 5 mols of ethylene and/or propylene oxide to fatty alcohols, sulfated fatty acid-monoglycerides, mono-fatty acid esters or mono-fatty alcohol ethers of dihydroxypropane-sulfonic acid, fatty acid esters of hydroxyethane-sulfonic acid, fatty acid amides of taurine or methyl taurine, sulfated adducts of l to 5, preferably of 1.5 to 4 mols of ethylene-and/or propylene oxide to alkylphenols, etc.

To the anionic tensides also belong synthetic carboxylates, such as amides of fatty acids and aminocarboxylie acids, particularly the corresponding derivatives of alanine or of sarcosine.

1n the washing agent cakes, according to the invention, soaps also can be present as anionic tensides, although their presence is not compellingly necessary for the improvement ofthe properties of the cake, particularly of the swelling properties toward water. If olefin sulfonates are used for the preparation of the cakes, according to the invention, in the hydrolysis of intermediaries, first formed during the sulfonation, which has been carried out with the use ofexcess alkali, soaps are necessarily formed if free fatty acids are added to the washing agent compositions as superfatting agents.

The shaped washing agents, according to the invention, can also contain nonionic tensides, but it is recommended, in view of the compactness properties of the shaped washing agents, not to increase their amount above 15 percent, preferably 10 percent by weight of the tenside mixture in the shaped washing agent, particularly if these nonionic tensides are present in an oily or pasty consistency at temperatures below 30C. If one wants to incorporate larger amounts of nonionic tensides, appropriate products should be selected which melt in the range of 4090C.

As nonionic tensides, adducts of ethylene oxide to alkylphenols, fatty alcohols, fatty acids, or fatty acid amides are suitable, which, for example, can contain in the molecule 5 to 80, preferably 8 to ethyleneoxide units. The melting points of these products rise on the one hand with the melting point of the starting material, and on the other hand with the amount of added ethylene oxide. In place of the derivatives prepared with the use of ethylene oxide, or together with them, mixed adducts of ethylene oxide, on the one hand, and propylene and/or butylene oxide, on the other hand,

can be used where the named alkylene oxides can be added in any sequence one after the other, or as a mixture,

The products known by their commercial names Pluronics or Tetronics are also usable as nonionic tensides. These products occupy a special place within the scope of the tensides insofar as they do not have to contain an alkyl radical of 8 to 18, preferably 12 to 16 carbon atoms. These alkyl radicals are replaced by polypropylene glycol, or polybutyleneglycol radicals. Such nonionic tensides are obtained from waterinsoluble polypropyleneglycols or from water-insoluble propoxylated lower aliphatic alcohols with l to 8, preferably 3 to 6 carbon atoms and/or from water-insoluble propoxylated alkylene diamines. These water-insoluble propylene oxide derivatives are ethoxylated with ethylene oxide until water soluble and coverted to the named nonionic tensides. Also, these types of nonionics are liquid or solid products at normal temperatures, and melt partly above 40C. Here, there is the possibility to select the suitable substance for the desired purpose.

Monoor dialkylolamides of fatty acids, particularly fatty acid monoor diethanolamides belong further to the nonionic tensides.

In each of the above numerated types of nonionics there are substances which are solid at normal temperatures and melt above 30C. The following list of such nonionics gives only examples, it does not claim to be complete.

Nonionics, solid at normal temperatures, of the type of ethoxylated fatty alcohols, fatty acids, or alkylphenols with straight-chain C to C alkyl radicals are, for instance, the adducts of 45 mols ofethylene oxide to 1 mol of coconut fatty alcohol; of 20, or 50 mols of ethylene oxide to 1 mol of tallow alcohol; and of 40 mols of ethylene oxide to 1 mol of oleyl alcohol; reaction products of 1 mol of palmitic acid with 40 mols of ethylene oxide or of 1 mol of stearic acid with mols of ethylene oxide as well as of 1 mol of an alkylphenol especially nonylphenol, with 25 to 50 mols of ethylene oxide.

Finally, the following commercial products are also solid nonionics which belong to the type ofPluronics or Tetronics (the first of the two figures in parentheses gives in the Pluronics, the molecular weight of the polypropyleneglycol radical and, in the Tetronics", the molecular weight of the ethylenediaminepropylene oxide adducts, while the second number gives the amount of the ethyleneoxide units in the product in percent by weight): Pluronic F 38 (950/80), Pluronic F 68 (1750/80), Pluronic F 77 (2050/70), Pluronic F 87 (2250/70), Pluronic F 88 (2250/80), Pluronic F 98 (2750/80), and Pluronic F 108 (3250/80); Tetronic 707 (2750/75), and Tetronic 908 (4000/85).

The washing agent cakes, according to the invention, may also contain amphoteric tensides of which some, particularly the below named compounds with carboxyl groups, possess anti-microbial properties.

To the amphoteric tensides, useable, according to the invention, belong, for instance, compounds of the following general formula:

R, NH (R NH R COOH,

wherein R, is a higher-molecular-weight alkyl, alkylphenyl, alkylphenoxyalkyl or alkyloxyalkyl radical. particularly a corresponding hydrocarbon radical with 6 to 18, preferably 8 to 14 aliphatic carbon atoms; R, is ethylene or propylene; x is a whole number from 1 to 6; and R is an aliphatic, aliphatic-aromatic or aromatic link with l to 8 carbon atoms, preferably R is alkylene, alkylphenylene, phenylalkylene and phenylene.

As examples, the following compounds can be named; dodecylaminopropyl-glycine, tetradecyl-aminoethyl-B- alanine, dodecyl-di (aminoethyl)-glycine, dodecyl- In this formula R, has the same meaning as in the preceding formula, R represents an ethyleneor propylene group, R and R are lower alkyl radicals, R is a lower molecular weight aliphatic link such as lower alkylene, and X is an ether oxygen atoms, or the -CONH- group. Examples for such compounds are lauryl-l,3-amidopropyl-dimethyl-aminoacetic acid, lauryl-oxyethyl-di-(hydroxyethyl)-aminopropionic acid, octyl-phenoxy-ethyl-di-(hydroxyetlhyl)-aminoacetic acid, and others.

To the amphoteric tensides useable, according to the invention, belong also sulfobetaines, which are, for example, obtained by reacting of dialkyl fatty amines (alkyl radical C to C fatty radical C to C preferably C to C with sultones, particularly with propane sultone and 1,3- or 1,4-butane sultone).

The anionic tensides contained in the shaped detergents, according to the invention, .are preferably present in the form of their alkali metal salts, particularly as sodium salts. If needed, there is also the possibility to incorporate them in the form of their water-soluble salts with amines, particularly with alkylolamines, such as mono-, di-, or triethanolamines. The amphoteric compounds can be incorporated as inner salts, as salts with the above named alkaline reacting compounds, or as salts with acids.

The detergent cakes, according to the invention, contain other non-tenside ingredients, customary in shaped detergents, such as super fatting agents, complexing compounds, disinfectants, microbicidal substances, brighteners, buffers for a slightly acidic pH, perfumes, dyes, etc.

As superfatting agents, water-insoluble fatty acids, fatty alcohols, mono-, di-, or triglycerides, fatty acid esters, particularly fatty acid esters with fatty alcohols, lanolin, Vaseline, etc. are suitable, preferably melting at temperatures from 30 to C, and particularly 40 to 70C. Further are useable as superfatting agents are the esterification products, described in German Pat. No. 1,165,574, from equimolecular amounts of a diester of 1 mol of citric acid and two mols of a fatty alcohol with to 20, preferably 12 to 18 carbon atoms and a pentaerythritol-diester of one mol of pentaerythritol and two mols of a fatty acid with 10 to 20, preferably 12 to 18 carbon atoms.

Preferably, the washing agent cakes of the invention contain from about 12% to 47% preferably from 18% to 40% by weight of superfatting agents melting at temperatures of from 30 to 80C, preferably from 40 to 70C. These are preferably fatty acids having from 10 to carbon atoms and an iodine number below 10, fatty alcohols having from 10 to 20 carbon atoms and an iodine number below 10, mono-, dior triglycerides of the above fatty acids, esters of the above fatty acids with the above fatty alcohols, lanolin, vaseline, the citric acid-difatty alcohol pentaerythritol difatty acid esterification product and mixtures of the above.

Many of the above described nonionic ethylene derivatives, fatty acid alkylolamides, and amphoteric tensides possess skin-pleasing properties. If such tensides are incorporated into the shaped washing agents, according to the invention, they can at the same time partially take the role of a superfatting agent. Also suitable as superfatting agents are products which differ from the above described nonionic alkylene oxide derivatives only in those that have an alkoxylation degree which is incomplete for water solubility. These are water-insoluble propylene oxide derivatives or ethoxylation products, optionally containing propylene and/or butyleneglycol radicals, in which the amount of the added ethylene oxide is insufficient for the water insolubility. Such water-insoluble nonionic compounds are, for instance, commercially available under the name Ucon Fluid.

In the shaped washing agents, according to the invention, water-soluble or water-insoluble dyes may be present. The water-insoluble dyes include here also the color pigments frequently used for the brightening of washing agent cakes. Besides such washing agent cakes may contain brighteners, particularly in case of white washing agent cakes. Finally, as stabilizers organic complexing agents can be added, and in addition frequently the incorporation of dirt carriers has proven useful.

The usable brighteners are mostly, if not exclusively, derivatives of the diaminostilbene sulfonic acid of the diarylpyrazolines, and of aminocoumarin.

Examples for brighteners from the class of the diaminostilbenesulfonic acid are compounds according to formula I:

In this formula R and R may be halogen atoms, alkoxyl groups, the amino group or radicals of aliphatic, aromatic or heterocyclic primary or secondary amines, as well as radicals of aminosulfonic acids, whereby the aliphatic radicals present in the above groups contain preferably 1 to 4, and particularly 2 to 4 carbon atoms, while the heterocyclic ring systems are mainly 5- or 6- membered rings. As aromatic amines preferably radicals of aniline, anthranilic acid or aniline sulfonic acid are used. Brighteners derived from diaminostilbene sulfonic acid are used mainly for cotton. The following products deriving from formula I are commercially available whereby R is the radical NHC H and R can be the following radicals: NH NHCH ,-N- HCH CH OH,-NHCH CH -OCH .N- I-ICH CH CH OCH I CH3-N-CH2-CH2OH.

In the formula II, R and R are hydrogen atoms, possibly alkyl or aryl radicals substituted by carboxyl-, carbamide-, or ester groups, R and R are hydrogen or short chain alkyl radicals, Ar and Ar are aryl radicals, such as, phenyl, diphenyl, or naphthyl and may have other substituents, such as, hydroxy-, alkoxy-, hydroxyalkyl-, amino-, alkylamino-, acylamino-, carboxyl-, carboxylic ester-, sulfonic acid-, sulfonamide-, and sulfonic groups, or halogen atoms. Commercially available brighteners of this type are derived from formula III whereby the radical R is the groups Cl,SO- -NH -SO -CH=CH and COOCH -CH- O-CH while the radical R is in all cases a chlorine atom. Also 9-cyanoanthracene is a polyamide brightener commercially available.

To the polyamide brighteners belong also aliphatic or aromatic substituted aminocoumarins, for example, the 4-methyl-7-dimethylamino-, or the 4-methyl-7- diethylaminocoumarin. Further usable as polyamide brighteners are the compounds l-(benzimidazolyl-2)- 2-(N-hydroxyethyl-benzimidazolyl-Z)-ethylene and 1-N-ethyl-3-phenyl-7-diethylaminocarbostyril. Suitable brighteners for polyester and polyamide fibers are the compounds 2,5-di-(benzoxazolyl-2')-thiophene and 1,2-di-(5 '-methyl-benzoxazolyl-2')-ethylene.

Insofar the brighteners, together with other ingredients of the invention products, are present as aqueous solutions or as pastes, and are converted into solids by heat drying, it is recommended to add organic complexing agents as stabilizers for the brighteners in amounts ofat least 0.1% preferably 0.2 to 1% by weight of the solid products.

To the organic complexing agents belong, for instance, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid,

9 polyalkylene-polyamine-N-polycarboxylic acid, and other known organic complexing agents. Also combinations of different complexing agents can be used. To the other known complexing agents belong also diand polyphosphonic acids of the following constitutions:

wherein R is alkyl and R is alkylene, both with 1 to 8, preferably 1 to 4 carbon atoms, X and Y are hydrogen or alkyl with 1 to 4 carbon atoms and Z is the groups -OI-I,NH or -NXR.

For a practical use above all the following compounds are of interest: methylenediphosphonic acid, 1 -hydroxyethane-1 ,1 -diphosphonic acid, 1- aminoethane-l,l-diphosphonic acid, amino-tri-(methylenephosphonic acid) methylamino or ethylaminodi-(methylenephosphonic acid) as well as ethylene diamine-tetra-(methylenephosphonic acid). All these complexing agents can be present as free acids, preferably as alkali metal salts.

lnto the washing agent cakes, according to the invention, such dirt carriers or soil suspending agents can be incorporated which have also been proposed as additions for powdery washing agents. For this watersoluble colloids, mostly organic, are suitable, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether-carboxylic acids or ethersulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also watersoluble polyamides, containing acidic groups, are suitable for this purpose. Furthermore, soluble starch preparations and other than the above named starch products can be used, such as degraded starch, aldehyde starch, gelatinized starch, etc. Also polyvinylpyrrolidone is usable.

The above named non-tenside addition products are preferably charged by weight of the total composition.

0.01% to 0.2%, preferably 0.015% to 0.1% by weight of brighteners 0.1% to 1%, preferably 0.2% to 0.5% by weight of organic complexing agents.

The shaped washing agents, according to the invention, are prepared in a conventional manner. The power necessary for the processing of the mass on rolls, in extruding presses, and in converting of the crude shaped pieces to the desired form can be changed by the water content of the mass. If, for the processing of a special mixture, a too large power expenditure should be required, the latter can be decreased by increasing the water content. In this event, the claimed upper limit of the water content can be surpassed however on storing the pieces dry and thus attain after some time the claimed water content.

The following specific examples are illustrative of the shaped washing agents and compositions of the invention without being limitative in any manner.

EXAMPLES For the preparation of the below described detergent cakes a sulfosuccinic acid-mono alcohol ester (Na-salt) was used which had been prepared from the C to C fraction of coconut oil alcohols. The olefin sulfonate was derived from a mixture of straight-chain a-olefins with 15 to 18 carbon atoms. This olefin mixture had been prepared by sulfonation of 1 mol of olefin with about 1.2 mols of gaseous sulfur trioxide, diluted with inert gas, hydrolysis of the crude: sulfonation product with the calculated amount of aqueous sodium hydroxide at temperatures of about 100C and bleaching of the sulfonate with the aid of hypochlorite. The mixture of the two sulfonates contained about 5% by weight of neutral salts (Na SO and NaCl), based on the anhydrous sulfonate mixture.

The mixed citric acid ester mentioned in the examples was an esterification product of one mol of citric acid tallow fatty alcohol-diester and one mol of pentaerythritol-coconut fatty acid diester.

For the preparation of the shaped detergent pieces, the ingredients in the given amounts were mixed in a kneader at temperatures of 60 to C, brought to the requried water content, homogenized on rolls and then extruded from vacuum extruders: in a strand of the cross-section of the customary commercial toilet-soap cakes. By cutting and pressing of these strands, products of the desired shape and size were obtained.

The detergent cakes were prepared from the composition given in the examples, whereby the quantitative data for the olefin sulfonate and the sulfosuccinic acid ester refer to the anhydrous technical product, i.e., they include neutral salts and unsulfonated olefin as well as unreacted fatty alcohol (about 1%).

EXAMPLE 1 65% by weight of a tenside mixture consisting of 57% by weight of olefin sulfonate 43% by weight of sulfosuccinic acid ester 16% by weight of a hardened tallow alcohol (Iodine 5% by weight of a coconut fatty acid (C fraction) 5% by weight of stearin (Iodine No.=2)

1% by weight of lanolin 1% by weight of lecithin 6% by Weight of water 1% by water of perfume EXAMPLE 2 55% by weight of a tenside mixture consisting of 33.3% by weight of olefin sulfonate 66.6% by weight of sulfosuccinic acid ester 20% by weight of stearin (Iodine No.=2)

14% by weight of tallow fatty alcohol (Iodine No.

2% by weight of lanolin 2% by weight of mixed citric acid ester 6% by weight of water 1% by weight of perfume EXAMPLE 3 60% by weight of a tenside mixture consisting of 30% by weight of olefin sulfonate 60% by weight of sulfosuccinic acid ester 10% by weight of coconut fatty acid diethanolamide l9 by weight of hardened tallow fatty acid (Iodine by weight of tallow fatty alcohol (Iodine No.

2 by weight of lanolin 2 by weight of mixed citric acid ester 1 by weight of perfume 0.03% by weight of brightener 0.1 by weight of TiO 0.3 by weight of hydroxyethanediphosphonate (sodium salt) residue water (5.57% by weight) EXAMPLE 4 70% by weight of a tenside mixture consisting of 50% by weight of sulfosuccinic acid ester by weight of olefin sulfonate 20% by weight of coconut fatty alcohol sulfate 10% by weight of soap 9 by weight of stearin (Iodine No.=2)

9 by weight of tallow fatty alcohol (Iodine No. l)

1 by weight of mixed citric acid ester 2 by weight of lanolin 0.1 by weight of TiO 0.003% by weight of dye residue water (8.897% by weight) The properties in use of the shaped detergents, according to the invention, show a remarkable similarity with soap. They differ, therefore, advantageously from the until now known shaped detergents on the basis of synthetic tensides even if those contain water-insoluble builders. Above all, their swelling behavior is largely identical to that of soap. On longer lying on a moist substrate, such as a soap dish of a wash basin, they indeed absorb water. This can be recognized by the bright discoloration, but they lose this water in dry surroundings without a noteworthy decrease in the compactness of the dried materials. The foam formed during washing is similar to that of soap both in its structure and in its behavior. The foam present in the wash basin collapses quickly on rinsing. The abrading observed in washing is largely identical to that of good toilet soap. People who wash or bathe with these cakes did not observe a disagreeable degreasing of the skin.

It should be kept in mind that the term builders is also used in the field of the detergent powders, where it means certain water soluble substances enhancing the washing action of detergents. In this case, however, the term builders designates a certain kind of water insoluble substances, usualy incorporated into soap pieces to improve their body properties when in contact with water.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be utilized without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. Shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from 55% to 80% by weight of a tenside mixture consisting essentially of I) from 70% to 100% by weight of said tenside mixture of a sulfonate mixture consisting essentially of (a) from 20% to 70% by weight of said sulfonate mixture ofa water-soluble salt ofa monoester of a sulfodicarboxylic acid selected from the group consisting of sulfoalkanedioic acids having 3 to 8 carbon atoms and sulfobenzenedicarboxylic acids, monoesterified with fatty alcohols having 8 to 18 carbon atoms, at least 50% of said fatty alcohols having 10 to 16 carbon atoms and (b) from 30% to 80% by weight of said sulfonate mixture of a water-soluble salt of a mixture of hydroxyalkane sulfonates, alkene sulfonates and alkane disulfonates, the individual components of said water-soluble salt ofa mixture of sulfonates having 10 to 18 carbon atoms, said water-soluble salts being selected from the group consisting of alkali metal salts and alkylolamine salts, and (2) from 0 to 30% by weight of said tenside mixture of tensides excepting said (a) and (b) selected from the group consisting of anionic surface-active compounds, non-ionic surfaceactive compounds and amphoteric surface-active compounds, (B) from 18% to 40% by weight ofnon-tenside water-insoluble superfatting agents melting at from 30C to 80C selected from the group consisting of fatty acids, fatty alcohols, monoglycerides of fatty acids, diglycerides of fatty acids, triglycerides of fatty acids, fatty acid esters of fatty alcohols, lanolin, vaseline, esters of 1 mol ofa citric acid difatty alcohol ester and 1 mol of pentaerythritol difatty acid ester and nonionic alkylene oxide derivatives having an alkoxylation degree which is incomplete for water solubility, and (C) from 5% to 10% by water.

2. The shaped washing agent of claim 1 wherein said sulfodicarboxylic acid is sulfosuccinic acid.

3. The shaped washing agent of claim 2 wherein said monoester of sulfosuccinic acid is with a primary alkanol having 12 to 14 carbon atoms. a

4. The shaped washing agent of claim 1 wherein the individual components of said water-soluble salt of a mixture of sulfonates has from 12 to 16 carbon atoms.

5. The shaped washing agent of claim 1 wherein said other tensides include up to 15% by weight ofnon-ionic surface-active compounds having a melting point of at least 30C.

6. Shaped washing agents based on synthetic detergents having a composition consisting essentially of(A) from 55% to 80% by weight of a tenside mixture consisting essentially of (I) from to 100% by weight of said tenside mixture ofa sulfonate mixture consisting essentially of (a) from 20% to 70% by weight of said sulfonate mixture of an alkali metal salt ofa monoester of sulfosuccinic acid monoesterified with a primary alkanol having 12 to 14 carbon atoms and (b) from 30% to by weight of said sulfonate mixture of an alkali metal salt of a mixture of hydroxyalkane sulfonates, alkene sulfonates and alkane disulfonates, the individual components of said alkali metal salt of a mixture of sulfonates having from 12 to 16 carbon atoms, and (2) from 0 to 30% by weight of said tenside mixture of tensides excepting said (a) and (b) selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, (B) from 18 to 40% by weight of superfatting agents melting at temperatures from 40 to 70C selected from the group consisting of fatty acids having from 10 to 20 carbon atoms and an iodine number below 10, monoglycerides of said fatty acids, diglycerides of said fatty acids, triglycerides of said fatty acids, fatty alcohols having from 10 to 20 carbon atoms and an iodine number below 10, esters of said fatty alcohols with said fatty acids, lanolin, vaseline, the esterification product from equimolar amounts of a diester ofcitric acid with a fatty alcohol having 10 to 20 carbon atoms and a diester of pentaerythritol with a fatty acid having 10 to 20 carbon (benzoxazolyl-Z)-thiophene and l,2-di-(5-methylbenzoxazolyl-2)-ethylene and from 0.1% to 1% by weight of organic complexing agents selected from the group consisting of nitrilotriace'tic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, polyalkylenepolyamine- N-polycarboxylic acids, diphosphonic acids and polyphosphonic acids, and their alkali metal salts.

Claims

2. The shaped washing agent of claim 1 wherein said sulfodicarboxylic acid is sulfosuccinic acid.
3. The shaped washing agent of claim 2 wherein said monoester of sulfosuccinic acid is with a primary alkanol having 12 to 14 carbon atoms.
4. The shaped washing agent of claim 1 wherein the individual components of said water-soluble salt of a mixture of sulfonates has from 12 to 16 carbon atoms.
5. The shaped washing agent of claim 1 wherein said other tensides include up to 15% by weight of non-ionic surface-active compounds having a melting point of at least 30*C.
6. Shaped washing agents based on synthetic detergents having a composition consisting essentially of (A) from 55% to 80% by weight of a tenside mixture consisting essentially of (1) from 70% to 100% by weight of said tenside mixture of a sulfonate mixture consisting essentially of (a) from 20% to 70% by weight of said sulfonate mixture of an alkali metal salt of a monoester of sulfosuccinic acid monoesterified with a primary alkanol having 12 to 14 carbon atoms and (b) from 30% to 80% by weight of said sulfonate mixture of an alkali metal salt of a mixture of hydroxyalkane sulfonates, alkene sulfonates and alkane disulfonates, the individual components of said alkali metal salt of a mixture of sulfonates having from 12 to 16 carbon atoms, and (2) from 0 to 30% by weight of said tenside mixture of tensides excepting said (a) and (b) selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds, (B) from 18% to 40% by weight of superfatting agents melting at temperatures from 40* to 70*C selected from the group consisting of fatty acids having from 10 to 20 carbon atoms and an iodine number below 10, monoglycerides of said fatty acids, diglycerides of said fatty acids, triglycerides of said fatty acids, fatty alcohols having from 10 to 20 carbon atoms and an iodine number below 10, esters of said fatty alcohols with said fatty acids, lanolin, vaseline, the esterification product from equimolar amounts of a diester of citric acid with a fatty alcohol having 10 to 20 carbon atoms and a diester of pentaerythritol with a fatty acid having 10 to 20 carbon atoms, and mixtures thereof, and (C) from 5% to 10% by weight of water.
7. The shaped washing agents of claim 6 having a further content of from 0.01% to 0.2% by weight of fabric brighteners selected from the group consisting of derivatives of diaminostilbene slfonic acids, derivatives of diarylpyrazoline, derivatives of aminocoumarins, 9-cyanoanthracene,1-(benzimidazolyl-2)-2-(N-hydroxyethyl-benzimidazolyl-2) -ethylene, 1-N-ethyl-3-phenyl-7-diethylaminocarbostyril, 2,5-di-(benzoxazolyl-2)-thiophene and 1, 2-di-(5-methyl-benzoxazolyl-2'')-ethylene and from 0.1% to 1% by weight of organic complexing agents selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, polyalkylenepolyamine-N-polycarboxylic acids, diphosphonic acids and polyphosphonic acids, and their alkali metal salts.