CA1040502A - Detergent composition - Google Patents

Abstract

DETERGENT COMPOSITION

John Michael Corkill and Bryan L. Madison ABSTRACT
Detergent compositions containing novel amorphous aluminosilicate ion exchange materials as builders are provided.
The amorphous aluminosilicate builders are characterized by the speed and efficiency with which they remove both calcium and magnesium hardness ions from water. Optionally crystal-line aluminosilicate ion exchange materials may also be uti-lized in said detergent compositions.

Description

It has long been recognized that laundry compositions function more efficiently in soft water than in water containing significant amounts of dissolved "hardness" cations such as calcium ion, magnesium ion and the like. Heretofore, laundry water has been softened prior to use, usually by passing the water through columns of zeolite or other cation exchange materials. The use of such zeolitic or other cation exchange materials to pre-soften water requires a separate tank or appliance wherein the water can be percolated slowly through the ion exchange material to remove the undesirable cations. Such pre-softening procedures require an additional expense to the user occasioned by the need to purchase the softener appliance.
Another means whereby fabrics can be optimally laundered under hard water conditions involves the use of water-soluble builder salts and/or chelators to sequester the undesirable ... ..
hardness cations and to remove them effectively from interaction with the fabrics and detergent materials in the laundering liquor.
.
However, the use of such water-soluble builders necessaril~ intro- ;-duces into the water supply certain materials which, in improperly treated sewerage effluents, may be undesirable. Accordingly, a means for providing water-softening builders in detergent composi- `
tions without the need for soluble builder additives is desirable.
~ variety of methods have been suggested for providing builder and water-softening action concurrently with the deterging cycle of a home laundering operation, but without the need for water-soluble detergent additives. One such method employs a phosphorylated cloth which can be added to the laundry bath to ;
sequester hardness ions and which can be remoyed after each laundering; see U.S. Patent 3,424,545.
The use of certain clay minerals to adsorb hardness ions from laundering liquors has also been suggested; see for

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example, Rao, in Soap Vol. 3 ~3 pp. 3-13 (1950); Schwartz, et al., "Surface Active Agents and Detergents", Vol. 2, p. 297 et ~. (1966).

The zeolites, especially the naturally-occurring aluminosilicate zeolites, have been suggested for use in washing compositions; see U.S. Patent 2,213,641; also U.S. Patent 2,264,103.
Various aluminosilicates have been suggested for use as adjuncts to and with detergent compositions; see, for example, U.S. Patents 923,850; 1,419,625; and British Patents 339,355;
461,103; 462,591; and 522,097.
The copending Canadian application of Corkill, Madison and Burns, S.N. 199,507, filed May 10, 1974, encompasses the use of complex crystalline aluminosilicates as sequestrants for calcium hardness. Corkill, et al., teach that auxiliary, water~
soluble builders can be co-present with the crystalline alumino silicates to additionally control magnesium hardness.
As can be seen from the amount of effort in this area, the need for an effective builder material which controls mixed hardness cations ~Ca+~ and Mg~+~ is substantial. To this end, insoluble ion exchange builders which quickly and effectivel~
reduce mixed cation hardness in a detergency ¢ontext are required. -To be optimally useful in laundry detergent composi-tions, a cation exchange builder material should have sufficient -cation exchange capacity to significantly decrease the hardness -~
of the laùndry bath without requiring excessive amounts of the ion exchanger. Moreover, the ion exchange material should act rapidly, i;e., it should reduce the cation hardness in an aqueous laundry bath to an acceptable level w~thin thé limited time (ca.

10 - 12 minutes) available during the deterging cycle of a home laundering operation. Optimally, effective ion exchange materials should be capable of reducing mixed calcium and magnesium hardness

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to about 1 to 2 grains per gallon within the first 1 to 3 minutes of the deterging cycle. Such cation exchange builders are desirably substantially water-insoluble, inorganic materials which present little or no ecological problems in sewage.
It has now been found that certain amorphous alumino-silicate materials have the high ion exchànge capacity, the rapid ion exchange rate and the efficacy with both Ca++ and Mg~+ hard-ness needed for use as optimal cation exchange builder materials in laundry detergent compositions.
Accordingly, it is an object of the present invention to provide detergent compositions containing insoluble, amorphous, inorganic aluminosilicate ion exchange materials which control both Ca++ and Mg++ hardness without the need for auxiliary builders other than the optional use of crystalline aluminosili~
cate.
It is a further object herein to provide methods for laundering fabr~cs using the aforesald detergent compositions.
These and other objects are obtained herein as will ~
be seen from the following disclosure. ~ -SUMMARY OF THE INVENTION
The present invention encompasses detergent composi-tions capable of rapidly reducing the free polyvalent metal ion content (especially Ca and Mg +) of an aqueous solution, comprising:
(a) from about 5% to about 95% (preferably about 20% to about 50%~ by wèight of a water-insoluble, amorphous, hydrated aluminosilicate ion-exchange builder material of the empirical formula Nax (xA102 . SiO2 ) wherein x is a number from 1.0 to 1~2 and further c~aracter~zed b~y a ~g~ exchange capacity of from about 50 mg eq. CaCO3fg. to about 150 mg eq.

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CaCO3/g. (anhydrous basis); and (b) from about 5~ to about 95~ (preferably about 15 to about 50%) by weight of a water-soluble organic detergent compound selected from the group consisting of anionic, ~onionic, ampholytic and zwitterionic detergents, and mixtures thereof.
(c) Optionally the detergent composit~on may contain crystalline aluminosilicate ion exchange material of the formula Nal2(AlO2 -sio2)12 xH2 wherein x is an integex of from about 20 to about 30 (preferably 27), said crystalline alumino-silicate ion exchange material characterized b~
a particle size of from about 1 micron to about 100 microns in diameter (preferably 1 micron to about 10 microns in diameter) and a calcium ion exchange capacity which is at least about 200 mg equivalent of CaCO3 hardness/gram of alumino-silicate, calculated on an anhydrous basis, and which generally lies within the range of from ~;
about 300 mg eq.~g to about 352 mg eq.~g~, and further characterized by a calcium ion exchange rate which is at least about 2 grains Ca+~
gallon/minute/gram of aluminosilicate anhydrous basis, and lies within the range of about 2 yrains/gallon/minute/gram to about 6 grains/- ~`
gallon/minut`e/gram, based on calcium ion hardness.
The level of the crystalline aluminosilicate 5nould not exceed a weight ratio of 4:1 relative to the amorphous aluminosilicate. - -DET~rLED DES~rPTION OF THE INVEN~ION

The detergent compositions of this invention comprise ~., .

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two essential components, the amorphous aluminosilicate builder and the water-soluble detergent componentl These components are described in detail as follows.
Aluminosilicate Builder The desirable mixed Ca++ and Mg++ sequestration properties of the amorphous aluminosilicates herein appear to be a function of several interrelated ~actors which result from their method of preparation. -One essential feature of the amorphous ion exchange builder material herein is that it be in the "sodium form". For example, it has surprisingly been found that the potassium and hydrogen forms of the instant aluminosilicate exhibit neither the exchange rate nor the exchange capacity necessary for optimal builder use.
~ second essential feature of the ion exchange builder materials herein is that they be in a hydrated form, i.e., contain about 10% to about 22% by weight of water. Highly preferred .
aluminosilicates herein contain the theoretical maximum of from about 18% to about 22~ (wt.) water in their crystal matrix. It has been found, for example, that less highly hydrated alumino-silicates, e.g., those with about 6~ water, do not function effectively as ion exchange builders when employed in the context of a laundry detergent composition.
Moreover, the amorphous alumLnosilicates herein are stable under processing conditions commonly employed in the preparation of spray-dried detergent compositions. That is to say~ the amorphous aluminosilicates herein retain their mixed hardness control properties e~en after heating to 50C - 100C.
This is unusual, inasmuch as other amorphous aluminosilicates lose their ion exchange properties upon heatingO
~ third essential feature of the ion exchange builder materials herein is their particle size range. The amorphous ~4a!5~
aluminosilicates herein inherently have a small (ca 0.01 micron to 5 micron) particle size. Such small particle size results in fast, highly efficient builder materials. Moreover, this small particle size accounts for the fact that the aluminosilicates herein do not noticeably deposit on the fabrics being laundered.
The method set forth below for preparing the alumino-silicates herein is specifically designed to prepare such mate-rials in the amorphous state. In particular, the process herein employs highly concentrated solutions which tend to favor rapid formation of amorphous particles. The concentrations of the solutions herein are limited only by the need to pour and effi-ciently mix the reactants.
Moreover, the process herein takes into consideration ;
all the essential elements disclosed above for preparing an effective aluminosilicate builder material~ First, the process avoids contamination of the aluminosilicate product by cations other than sodium. Second, the process is designed to form the aluminosilicate in its most highly hydrated form. Hence, high `
temperature heating and drying are avoided. Third, the process is designed to form the aluminosilicate materials in a finely-divided state having a narrow range of small particle sizes. Of course, additional gxinding operations càn be employed to still further reduce the particle size. However, the need for such mechanical reduction steps is substantially lessened by following the process herein.
The chemical reactions involved in the preparation of the aluminosilicates of this invention are complex, due to the multiple possible reactions which can occur upon admixture of aluminate and silicate in an aqueous, basic medium. Under the reaction conditions employed herein, the reactants appear to first form an amorp~ous aluminosilicate mater~al, which unclergoes further transformation be~ore being con~erted into a crystalline .:
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aluminosilicate. The amorphous crystalline conversion is thus not step-wise, but ooc~rs throughout the process, inasmuch as the system of reactants is in a dynamic state. While, in theory, it should be possible to admix the reactants, quench the reaction at the appropriate point, and secure only the desired amorphous aluminosilicate, this is not feasible in lar~e~scale preparations.
In practice, the process herein is designed to prepare mixtures of the amorphous and crystalline aluminosilicates and to stop the reaction at a point where a substantial portion (ca. 50%, and greater) of the amorphous materials have not yet been converted to the crystalline form. The use of highly concentrated mixtures of reactants and care~ul control of reaction times, all in the manner hereinafter disclosed, achieves these desirable results.
Following preparation o~ the mixed ar,lorphous~crystalline materials herein, the mixtures can be separated by suspension in water, whereby the crystalline material settles and the amorphous mate-rial remains suspended.
The aluminosilicate ion exchange builder-softening materials herein are prepared according to the following procedure:

(a) Admix sodium aluminate (NaA102) and sodium hydroxide in water to form a mixture having the following (preferred) weight ratios of the components:
H2O!NaAlO2 = 2.9:1 H2O/NaO~I = 5.2:1 NaAlO2/NaOH = 1.8:1 If prepared at lower temperatures, the mixture of aluminate and sodium hydroxide is not a true solution and may contain a small quantity of finely dispersed partlculate materials. The temperature of the mixture is ~djusted to about 2noc ~ 70~C, ~referabl~ about 50DC.

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(b) Add a sodium silicate solution (ca. 37% wt. solid;
3.2:1 SiO2/Na2O ratio) rapidly to the mixture of step (a?. This rapid mixing step can be carried out using a vessel employed with an `~,efficient agitator; alternatively, the two mixtures at the desired temperature can be metered into an inline mixer which can be part of a dominant bath system to provide a continuous process. The ratio of NaAlO2 to sodium silicate (anhydrous basis) is about 1.6:1 which is an excess of NaAlO2 relative to the composition of the aluminosilicate builder material.
(c~ Heat the mLxture of step (b) rapidly to 75~C to 95C (preferably 80C ~ 85C) and maintain at this temperature for 10 minutes to 60 minutes (preferably 10 minutes - 20 minutes). ;
(d) Cool the slurry from step (c) to about 50C and filter. Recover the resulting filter cake and wash in water using a sufficient quantity of water to yield a wash water/solids (anhydrous basis) weight ratio of about 2.0:1 (preferred). -~
Repeat the filtration and washing operations.
The filter cake prepared by the ~oregoing process comprises a mixture of crystalline aluminosilicate and amorphous aluminosilicate in approximately a 1:1 (wt.) ratio.
The amorphous aluminosilicate of this invention may be ~J'`'~` '.
separated from the amorphous-crystalline mixture prepared in the foregoing manner ~y sLmply suspending the filter cake mixture in water. When thus ~uspended, the crystalline portion of the mix settles out (over a period of about 1-6 hours), whereas the amorphous material remain~ suspended in t~e a~ueous medium. The ~.
amorphous material can be separated by decantation or othler _g_ `

. .. . . . . .

z physical means. Of course, low speed centrifugation can be employed to more rapidly separate the amorphous component from ~;
the crystalline component of the mixtures herein.
For use in powdered or granular detergent compositions, it is preferred to dry the recovered amorphous aluminosilicate to a moisture content of from about 10% to ahout 22% by weight using a drying temperature below about 175C to avoid excessive dehydration. Preferably, the drying is performed at 100C to 105C.

The amorphous material prepared in the foregoing manner has an irregular structure which is not amenable to analysis by x-ray diffraction.
The amorphous aluminosilicate ion exchangers herein are ~urther characterized by their calcium ion exchange capacity which is at least about 200 mg equivaIent of CaCO3 hardness/gram of aluminosilicate, calculated on an anhydrous basis, and which generally lies within the range of about 300 mg eq./g. to about 352 mg eq./g.
The ion exchange materials herein are further charac-terized by their calcium ion exchange rate which is at leastabout 2 grains (Ca++)/gal./min./g.`of aluminosilicate (anhydrous basis), and lies within the range of about 2 gr.~gal./min.~g. to about 6 gr.~gal./min.~g., based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a Ca~+ exchange rate of at least about 4 gr.~gal./min.~g.
The al~minosilicate ion exchangers herein are further characterized by their magnesium exchange capacity, which is at least about 50 mg. eq. of CaCO3 hardness/gram of aluminosilicate, calculated on an anhydrous basis, and which generally lies within the range of about 50 mg. eq.~g. to 150 mg. eq./g.
The ion exchange materials herein are still further charac~erized ~y t~eir magnesium ion exchange rate which is at -10- ' ~4~50;2 least about 1 grain (Mg )/gal./min./g. of aluminosilicate (anhydrous basis), and lies within the range of 1 gr.~gal./min./g.
to about 3 gr./gal./min./g., based on magnesium ion hardness.
Optimum aluminosilicates for builder purposes exhibit a magnesium exchange rate of at least about 2 gr./gal./min./g.
The ion exchange properties of the aluminosilicates herein can conveniently be determined by means of a calcium ion electrode and a divalent ion electrode. In this technique the rate and capacity of Ca~+ and Mg++ uptake from an aqueous solu-tion containing a known quantity of Ca~+ and Mg++ ions are deter-mined as a function of the amount of aluminosilicate ion exchange material added to the solution. More specifically, the ion exchange rate of the amorphous aluminosilicates is determined as follows. The aluminosilicate prepared in the foregoing manner is added in the sodium form to 150 ml. of aqueous solution con-taining 4.7 gr./gal. Ca++ and 2.4 gr./gal. Mg++ (measured as CaCO3) at a concentration of 0.06% (wt.), pH of 10.0, and with -gentle stirring of the solution. The rate of calcium depletion is measured using the calcium electrode (commercially available;
"Orion"*) and the rate of total calcium and magnesium depletion is determined using the general divalent cation electrode. Mag-nesium ion removal is thereafter determined by the difference in readings. The rate of depletion is determined for each cation by taking measurements at appropriate time intervals. Total depletion from the solution is calculated after ten mlnutes, which corrèsponds to the normal wash time in an aqueous laundering process. Rate curves for calcLum depletion, magnesium depletion and mixed calcium and magnesium depletion can be plotted as gr./gal. v. time.
Calcium exchange capacity of the aluminosilicat~es herein can be determined by a simple titration method, In prac-tice the aluminosilicate sample is equ~librated ~ith a known *Trademark --11-- .

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~L~4~5~)2 excess of Ca . After equilibration and uptake of the calcium ion, the excess calcium ion remaining in solution is determined by a standard ti~ration with EDTA, using a standard Eriochrome Black T Indicator. Magnesium ion capacity is determined titri-metrically, in similar fashion.
The following example is a typical pilot plant scale preparation of the amorphous aluminosilicate ion exchange builder herein. As noted hereinabove, the amorphous aluminosilicate can be readily removed from the crystalline aluminosilicate by suspending the filter cake in water. The crystalline port:ion of the mixture settles out (ca. 1 to 6 hours' standing) and the amorphous portion remains suspended in the water. The portions can be separated by decanting or other mechanical means.
EXAMPLE I
A typical charge used in the pilot plant was as follows:

Wt.%
As Is(Anhyd.) Water 212.8 lb. 64.29 Sodium Aluminate 115.4 lb. 16.40 Sodium Hydroxide (50% aqueous)109.9 lb. 9.05 Sodium Silicate (3.2:1165.0 lb.10.26 sio? :Na2O ratio; ca. 50~ wt.
aqueous solution) The pilot plant consisted of a baffled 55 gallon insulated reaction vessel having a "Lightnin"'* propeller-type mixer and a side arm heat exchanger equipped for recirculation and fed by a gear pump. The pump had a rated capacity of 5 gallons per minute. The discharge stream from the reactor passed through another heat exchanger which cooled the stream which was then fed to a vacuum rotary filter. Cake from the filter fell into a tank equipped With a ~'Lightnin~' propeller~type mixér ~here the cake ~as re~urri`ed w~th wash ~ater. The slu;rry was *Trademark :~L0405~2 then fed to a vacuum rotary filter and the cake recovered or rewashed, as desired. Auxiliary equipment included a metering pump used to feed the silicate raw material solution at a desired rate.
The water was charged to the reaction vessel followed by the sodium aluminate and the sodium hydroxide. The mixture was agitated until the aluminate was "dissolved". The tempera-ture was ad~usted to 50C. The sodium silicate at 50C was then metered into the aluminate-lye solution at a rate of about 35 lb./min. Maximum agitation was required at this stage of the operation to prevent solidification of the slurry. The slurry ~ `
was agitated for a period of about 15 minutes to break up lumps and to assure complete contact between reactants. The slurry was then passed through the side arm heat exchanger and the tempera-ture was raised to about 80C - 100C, and maintained at this range for about 1 hour. The slurry was then passed through a heat exchanger, cooled to about 37C and filtered. The cake was water-washed several times.
The amorphous aluminosilicate was separated from the crystalline by suspension of the mixed filter cake material in water for a period of about ~ hours. The amorphous material was dried (ca. 105C). The amorphous aluminosilicate prepared in the foregoing manner had the empirical formula Nax (xA102 SiO2 ) wherein x is a number from 1.0 to 1.2 and was characterized by a Mg~ exchange capacity of about 125 mg eq. CaCO3/gram of aluminosilicate (anhydrous basis), and contained about 20% by weight of water (i.e., fully hydrated)O
The amorphous ion exchange materials prepared in the foregoing manner can be employed in laundering liquors at levels of from about 0,0~5% to about 0.25% by weight of the liquor, and ;~
reduce the hardness level, particularly m~xed calcium and magne-~04~S1~2 sium hardness, to a range of about 1 to 3 grains/gallon within about 1 to about 3 minutes. Of course, the usuage level will depend on the original hardness of the water and the desires of the user. Highly preferred detergent compositions herein comprise from about 20% to about 50% by weight of the aluminosilicate builder and from about 15% to about 50% by weight of the water-soluble, organic detergent compound. Alternately, the crystalline aluminosilicate is not removed ~efore drying and a detergent com-position is prepared with a mixture of amorphous and crystalline 1~ aluminosilicates.

DETERGENT COMPONENT
The detergent compositions of the instant invention can contain all manner of oryanic, water~soluble detergent com-pounds, inasmuch as the aluminosilicate ion exchangers are compatible with all such materials. A typical listing of the classes and species of detergent compounds useful herein appear in U.S. Patent 3,664,961. The following list of detergent com-pounds and mixtures which can be used in the instant compositions is representative of such materials, but is not intended to be limiting.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful as the detergent component of the composition herein. This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatt~ acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Anot~er class of detergents includes water-so:Luble ~, .

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salts, particularly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group. (~ncluded in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic detergents which form a part of the detergent compositions of the present invention are the sodium and potassium alkyL sulfates, especially those obtained by sulfating the higher alcohols (C8 - C18 carbon atoms~ produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chair or branched chain configuration, e.g., those of the type described in United States Patents 2,~20,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 13 carbon atoms, abbreviated as C13 LAS.
Other anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates;
and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate contàining about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
Water-soluble nonionic synthetic detergents are also useful as the detergent component of the instant composition.
Such nonionic detergent materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The :Length of th~ p~lyQxyalkylene ~roup which is co~den~ed with any paxticular ~4e~s~9z hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements For example, a well-known class of nonionic synthetic detergents is made available on the market under the trademark of "Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. Other suitable nonionic synthetic detergents include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ~;
ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The water-soluble condensation products of aliphatic alcohols haying from 8 to 22 carbon atoms, in either straight chain or branched configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergents include water-soluble amine oxides containlng one alkyl moiety of from about 10 to 28 ..... . . ..
carbon atoms and 2 moieties selected from the group consisting ;
of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 28 carbon atoms and 2 moieties selected Erom the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms;
and water-soluble sulfoxide detergents containin~ one alkyl moiety of from about 10 to 28 car~on atoms and a moiety selected from the group cons`~tl'ng of alkyl and hydraxyal~yl moieties oE from ;'~':' ... : . . ..
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1 to 3 carbon atoms.
Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium com-pounds in which the aliphatic moieties can be straight chain orbranched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group.
Other useful detergent compounds herein include the water-soluble salts of esters of a-sulfonated fatty acids con-taining from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide;
water-soluble salts of olefin sulfonàtes containing from about 12 to 24 carbon atoms; and ~-alkyloxy alkane sulfonates con-taining from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Preferred water-soluble organic detergent compounds herein include linear alkyl benzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; the tallow range alkyl sulfates; the coconut alkyl glyceryl sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 14 to 18 carbon atoms and ~herein t~e a~erage degree of etho~ylation Yaries between 1 and 6; the sulfated condensation products of tallow `~
alcohol with from about 3 to 10 moles of ethylene oxide; olefin sulfonates containing from about 14 to 16 carbon atoms; al~yl ~ -dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethyl-ammonio-propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy-propane-sulfonates wherein the alkyl group in both types contains from about 14 to 18 carbon atoms; soaps, as hereinabove defined; the condensation product `-of tallow fatty alcohol with about 11 moles of ethylene oxide;
and the condensation product of a C13 (avg.) secondary alcohol ;~
with 9 moles of ethylene oxide.
Specific preferred detergents for use herein include:
sodium linear C10 - C18 alkyl ben2ene sulfonate; triethanolamine C10 - C18 alkyl benzene sulfonate; sodium tallow alkyl sulfate;
sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with from about 3 to about 10 moles of ethylene oxide; the condensation ~ ~ .
product o~ a coconut fatty alcohol with about 6 moles of ethylene ' oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkyl- `~
ammonio~-2-hydroxypropane-l sulfonate, 3-(N,N~dimethyl~N-coconut-alkylammoniol-propane-l-sulfonate; 6~(N~dodecylbenzyl-N,N-dLmethyl-ammonio~hexanoate; dodecyl dimethyl amine o~ide; coconut alkyl dimethyl amine oxide; and the water-soluble sodium and potassium salts of higher fatty acids containing 8 to 24 carbon atoms~ -It is to be recognized that any of the foregoing deter-gents can be used separately herein or as mixtures. Examples of ;~
preferred detergent mixtures herein are as follows.
An especially preferred alkyl ether sulfate detergent -component of the instant compositions is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide.
Specifically, such preferred mixtures comprise from about 0.05% to 5% by weight of mixture of C12_13 compounds, from about 55~ to 70% by weight of mixture of Cl~ 15 compounds, from about 25~ to 40% by weight of mixture of C16 17 compounds and from about 0.1% to 5% by weight of mi~ture of C18 19 compounds.
Further, such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of mixture of compounds having a degree of ethoxylatiorl from 1 to 4, from about 12% to 22~ by weight of mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0.5%
to 10% by weight of mixture of compounds having a degree of ethoxyIation greater than 8.
Examples of alkyl ether sulfate mixtures falling within the above-specified ranges are set forth in Table I.

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~ 05~Z
Preferred "olefin sulfonate" detergent mixtures utilizable herein comprise olefin sulfonates containing from about 10 to about 24 carbon atoms. Such materials can be pro-duced by sulfonation of ~-olefins by means of uncomplexed sulfur dioxide followed by neutralization under condLitions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulfonates. The ~-olefin starting materials preferably have from 14 to 16 carbon atoms. Said pre.ferred ~olefin 5ul-fonates are described in U.S. Patent 3,332,880.
Preferred ~-olefln sulfonate mixtures herein consist essentially of from about 30% to about 70% by weight of a Component A, from about 20% to about 70% by weight of a Component B, and from about 2% to about 15% of a Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water~soluble salts of alkene-l-sulfonic acids containing from about lO to about 24 carbon atoms, said mixture of positional isomers including about lO~ to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of gamma-delta unsaturated isomer, and about 5~ to about 10% of a delta-epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds contain-ing from about lO to about 24 carbon atoms, the functional units being hydroxy and sulfonate groups wîth the sulfonàte groups always being on the terminal carbon and the hydroxyl group being .attached to a carbon.atom at least two carbon atoms removed from the terminal car~on atoms at

4~)SQ2 least 90% of the hydroxy group substitutions being in 3, 4 and 5 positions; and (c) said Component C is a mixture comprising from about 30~-95% water~soluble salts of alkene :
disulfonates containing from about 10 to about 24 ..~
carbon atoms, and from about 5% to about 70% ... : .
water-soluble salts of h~droxy disulfonates containing from about 10 to about 24 carbon atoms, ::
said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an inter:nal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the . .

terminal carbon atom and about the seventh carbon `.
atom, said hydroxy disulfonates being saturated.
aliphatic compounds having a.sulfonate group .. ::
attached to a terminal carbon, a second sulfonate ~ ~
group attached to an internal carbon atom not ~ .

more than about six carbon atoms removed from .
said terminal carbon atom, and a hydroxy group .
attached to a carbon atom which is not more than .. :
about four carbon atoms removed from the sîte of attachment of said second sulfonate group.
Optional Additives -.
_ _ The detergent compositions of the present invention ~ .
can contain, in addition to the aluminosilicate ion exchange builders, auxiliary, water-soluble builders such as those com- ;
monly taught for use in detergent compositions. Such auxiliary builders can be employed to aid in the .se~uestration of hardness ions and to help adjust the pH of the laundering liquor. Such auxiliax~ builders can be employed ~n.concentrations of ~rom '`~ ' ~4~50;2 about 5% to about 50% by weight, preferably from about 10% to about 35~ by weight, of the detergent compositions herein to provide their auxiliary builder and pH-controlling function.
The auxiliary builders herein include any of the conventional inorganic and organic water-soluble builder salts.
Such auxiliary builders can be, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphatès, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphatesl and hexametaphosphates. The polyphosphonates specifically include, for example, the sodium and potassium salts of ethylene diphos-phonic acid, the sodium and potassium salts of ethane l-hydroxy-l, l-diphosphonic acid and the sodium and potassium salts of ethane-1, 1, 2-triphosphonic acid. Examples of these and other phos-phorus-containing builder compounds are disclosed in U.S. Patents , 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176 and 3,400,148.
Non-phosphorus containing sequestrants can also be selected for use herein as auxiliary builders.
Specific examples of non-phosphorus, inorganic auxi-liary detergent builder ingredients include water~soluble inorganic carbonate, bicarbonate, and sil;cate salts. The alkali metal, e.g., sodium and potassium, carbonates, bicarbon-ates, and silicates are particularly useful herein.
Water-soluble, organic auxiliary builders are also useful herein. For example, the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful auxiliary builders in the .
present compositions. Specific examples of the polyacetate and polycarboxylate builder salts include ~odium, potassium~ lithium, ammonium and su~stituted ammoniu~ salts of eth~lene diamine '' :

.23~ : ~

1~4~5~Z
tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
Highly preferred non-phosphorus au~iliary builder ~ -materials herein include sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, and sodium ethylenediamine-tetraacetate, and mi~tures thereof.
Other highly preferred auxiliary builders herein are -~
the polycarboxylate bui]ders set forth in U.S. Pàtent 3,308,067, Diehl. Examples of such materials include the water~solub:Le salts of homo- and co-polymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic aci~ and methylenemalonic acid.
Additional, preferred auxiliary builders herein include the water-soluble salts, especially the sodium and potassium salts, of carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate and phloroglucinol trisulfonate.
The detergent composi~ïons herein can contain all manner of additional materials commonly found in laundering and cleaning compositions. For example, the compositions can contain thickeners and soil suspending agents such as carboxymethyl-cellulose and the like. Enzymes, especially the proteolytic and lipolytic enzymes commonly used in laundry detergent compositions can also be present herein. Varlous perfumes, optical bleaches, fillers, anti-caking agents, fabric ~ofteners and the like can be present in the compositions to provide the usual benefits occasioned by the use of such materials in detergent compositions.
It is to be recognized that all such adjuvant materials are use-ful herein inasmuch as they are compatihle and stable in thepresence of thè al~minosil~cate ion exchan~e ~uilders.
The detergent compositions of this invention can be , ~o~so~
prepared by any of the several well known procedures for p~e-paring commercial detergent compositions. For example, th~
compositions can be prepared by simply admixing the alumino-silicate ion exchange material with the water-soluble organic detergent compound. The optional builder material and adjuvant ingredients can be simply admixed therewith, as desired. Alter-natively, an aqueous slurry of the aluminosilicate ion exchange builder containing the dissolved, water-solùble organic detergent compound and the optional and auxiliary materials can be spray-dried in a tower to provide a granular composition. The granulesof such spray-dried detergent compositions contain the alumino-silicate ion exchange builder, the organic detergent compound and the optional materials.
Alternatively, the aluminosilicate ion exchange materials herein can be employed separately in aqueous laundry and/or rinse baths to reduce hardness cations. When so employed, the user can simply admix an effective amount, i.e., an amount sufficient to lower the hardness to about 1 to 2 grains per gallon, to the aqueous bath and thereafter add any commercial detergent compo--20 sition of choice. Generally, when employed in this manner the amorphous aluminosilicate will be added at a rate of about 0.005%
to about 0.25% by weight o~ the aqueous bath.
The ion exchange aluminosilicates herein can also be employed in combination with standard cationic fabric softeners in fabric rinses. When so employed, the aluminosilicates remove the hardness cations and result in a softer feel on the softened fabrics. Typical cationic fabric softeners useful in combination with the aluminosilicate ion exchangers include tallowtrimethyl- -ammonium bromide, tallowtrimethylammonium chlorLde, ditallow-dimethylammonium bromide, and ditallowdimethylammonium chloride.
Aqueous fahric softener compositions containing the alumino-silicate ion exchangers comprise from about 5% to about 95% by weight of the amorphous aluminosilicate herein and from about 1% to about 35% by weight of the cationic fabric softener.
The detergent compositions herein are employed in aqueous liquors to cleanse surfaces, especially fabric surfaces, using any of the standard laundering and cleansing techniques.
For example, the compositions herein are particularly suited for use in standard automatic washing machines at concentrat;ons of , from about 0.01% to about 0.50% by weight. Optimal results are `
obtained when the compositions herein are employed in an aqueous laundry bath at a level of at least about 0.10~ by weight. As in the case of most commercial laundry detergent compositions, `
the dry compositions herein are usually added to a conventional aqueous laundry solution at a rate of about 1.0 cup/17 gallons of wash water.
While the aluminosilicate ion exchange builder materials herein function to remove calcium and magnesium hardness ions over a wide pH range~ it is preferred that detergent compositions ~-containing such materials exhibit a pH in solution at a concen- ~ ;
tration of about 1.2% in the range of from about 8.0 to about 11, preferably about 9.5 to about 10.5. As in the case of other ;
standard detergent compositions, the compositions herein function optimally within the basic pH range to remove soils and triglyc-eride soils and stains. While the aluminosilicates herein inherently provide a basic solution, the detergent compositions comprising the alu~inosilicate and the organic detergent compound can additionally contain from about 5% to about 25% by weight of a pH adjusting agent. Such compositions can, of course, contain the optional water~soluble builders and adjuvants, as hereinbefore , described. The pH adjusting agents used in such compositions are selected such that the pH of a 0.05% by w~ight aqueous mix-ture of said composition is ln the range of ~rom about 9.5 to about 10.5.

~4(~5~Z
The optional pH adjusting agents useful herein include any of the water-soluble, basic materials commonly employed in detergent compositions. Typical examples of such water-soluble materials include the sodium phosphates; sodium silicate; sodium hydroxide; potassium hydroxide; triethanolamine; diethanolamine;
ammonium hydroxide and the like. Preferred pH adjusting agents herein include sodium hydroxide, triethanolamine and sodium silicate.
The following examples are typical of the detergent compositions herein, but are not intended to be limiting thereof.

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The foregoin~ composition provides excellent fabric laundering performance when employed under conventional home laundering conditions in a laundering liquor of 7 grains/gallon mixed Mg++/Ca~ hardness with a composition concentration in .
the laundering liquor of about 0.12~ ~y weig:ht. Under such conditions sudsing and cleansing performance of the Example'II '~
composition compares favo'rably with that of conventional, fully built, high-sudsing anionic detergent formulations. Such a composition i5 pourable and is prepared with conventional spray~ :
drying apparatus.
Compositions of substantially similar performance .;'~
quality are secured when, in the above-described Ex~mple II
composition, the sodium tallow alkyl sulfate is replaced with an ' equivalent amount of potassium tallow alkyl .sulfate, sodium ..
coconut alkyl sulfate, potassium coconut alkyl sulfate, sodium decyl benzene sulfonate, sodium undecyl benzene sulfonate, sodium ; .
tridecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, . ~
sodium tetrapropylene benzene sulfonate, potassium decyl benzene ' ~ .
sulfonate, potassium undecyl benzene sulfonate, potassium tridecyl benzene sulfonate, potassium tetradecyl benzene sulfonate and ..
potassium tetrapropylene benzene sulfonate, respectively.
Compositions of substantially similar performance quality, physical characteristics and processability are secured .
when, in the above-described Example II composition, the conden- ' sation product of the 15 carbon atom secondary alcohol with 9 .
moles of ethylene oxide is replaced with an equivalent amount of the condensation product of tridecyl alcohol with about 6 moles of ethylene oxide (HLB = 11.4); the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxicle (HLB = 12.01, `'Neodol.23~6.5'`* (HLB - 12i; '`Neodol 25-9"** ..
lHLB ~ 13.11; and ~.Tergitol 15~S~9~'*** ~HLB ~ 13.31, re~pectively. ~; .

* Trademark ~ '` '' ** Trademark .`. .
*** Trademark of Vn~on Carbide Corporat~on -29- .'' ,.r~

~o~soz EXAMPI.E III
A spray-dried detergent composition useful in water containing both Ca~ and Mg hardness is prepared having the following composition:
Component Wt.~
Surfactant System comprising: 24.7%
Sodium linear alkyl benzene sulfonate wherein the alkyl group averages about 11.8 carbon atoms in length 20% ~t. ratio anionic/
Condensation product nonionic =
of one mole of coconut 4.26:1 fatty alcohol with about 6 moles of ¦ :
ethylene oxide 4.7%J
*Amorphous aluminosilicate 25.0%
Sodium silicate ~Na2O/SiO2 15.0 wt. ratic = 1:2.4) Sodium sulfate 20.0%
Sodium acetate 5.
Sodium toluene sulfonate 2.0%
Water 4.0%
Minors Balance *Prepared in the manner disclosed in Example I. ~:

z The composition of Example III provi~es excellent fabric cleansing performance when employed under conventional home laundering conditions in a laundering liquor of 7 grains/-gallon mixed Ca++ and Mg hardness with a composition concentra~
tion in said laundering liquor of about 0.1~% by weight. The composition pH in solution is ca. 10.2 at this concentration.
Under such conditions, sudsing performance of the Example III
composition compares favorably with that of conventional, fully-built, high-sudsing anionic detergent formulations. Such a com-position is readily pourable and storage stable and is preparedwith conventional spray-drying apparatus.
Compositions of substantially similar performance quality, physical characteristics and processability are secured when, in the above compositions, the sodium silicate is replaced by an equivalent ~nount o~ sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylenediaminetetra-acetate, sodium polymaleate, sodium polyitaconate, sodium poly-mesaconate, sodium polyfumarate, sodium polyaconitate, sodium polycitraconate, sodium polymethylenemalonate, and mixtures thereof, respectively.
A composition of substantially similar performance quality, physical characteristics and processability is secured when, in the above described Example III composition, there is incorporated aboùt 3~ by weight of sodlum perborate solids with all other components remaining in the same relative proportions.
Such perborate compositions are particularly adapted for use under the washing conditions commonly encountered in Europe.
In the above composition the total surfactant system is replaced by an equivalent amount of the alkyl ether sulfate mixtures I, II, III and 1~ appearing in Ta~le I, respectively, and excellent detergency performance is secured.

' . ~ , .. .

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EXAMPLE IV
A phosphorus-free detergent composition is prepared having the following composition:
Component Wt.
*Surfactant System 35%
Triethanolamine (pH-adjusting agent) 7 NaOH (pH-adjusting agent) 0.5%
**Amorphous Aluminosilicate 35 Sodium Sulfate 15%
Water and Minors Balance *The Surfactant System comprises an a,olefin sulfonate mixture consisting essentially of from about 30% to about 70% by weight of a Component A, from about 20~ to about 70% by weight of a Component B, and from about 2~ to about 15% of a Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-l-sulfonic acids con-taining from about 10 to about 24 carbon atomq, said mixture of po~itional isomers including about'l0% to about 25% of an alpha-beta unsaturated isomer, about 3~ to about 70~ of a beta~gamma unsaturat~d isomer, about 5% to about 25% of gamma-delta unsaturated isomer, and about 5% to about 10% of a delta- ~ :
epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bifunctionally-substituted :
sulfur-containing saturated àliphatic com-pounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate groups with the sul-fonate groups always being on the terminal carbon and the hydroxyl group being at~ached to a carbon atom at least two carbon atoms removed from thè terminal carbon atoms at least 90~ of the hydroxy group substitutions being in 3, 4 and 5 positions; and (c) said Component C is a mixture comprising from about 30~-95% water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing rom about 10 to about 24 carbon atoms said :
alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than a~out six carbon atoms remo~ed from sa~d term~nal car~on atom, the alkene double bond being distributed ~etween ~he terminal carbon atom and about the ~L~4~S~Z :
seventh carbon atom, said hydroxy disul- :.
fonates being saturated aliphatic compounds .having a sulfonate gr~up attached to a terminal carbon, a second sulfonate group attached to an internal car~on atom not ::
more than a~out six carbon atoms removed ~::
from said terminal carbon atom, and a hydrox~ group attached to a carbon atom which is not more than about four carbon atoms removed from the site of atta~hment ~-.
of said second sulfonate group.

**Prepared as disclosed in Example I, here;nabove.
The composition of Example IV is added to an aqueous ....
bath at 110F at a rate of 0.15% by weight and used to launder ..
o~ly fabrics. Excellent cleaning results are secured under .;.
initial water hardness conditions of 7-12 gr./gallon mixed hardness. ~:~
In the above composition the surfactant system is replaced by an equivalent amount of.sodium linear C10-Cl8 alkyl `
benzene sulfonate; sodium tallow alkyl sulfate; sodi~m coconut alkyl glyceryl ether sulfonate; the sodium salt of sulfated .
condensation product of a tallow alcohol with from about 3 to : :
about 10 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles ~ -of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2- .
hydroxypropane-l-sulfonate; 3~N,N-dimethyl-N-coconutalkylammonio~--propane-l-sulfonate, 6-(N-dodecylbenzyl-N,N-dimethylammonio)- ..
-hexanoate; dodecyl dimethyl amine oxide; coconut alkyl diméthyl ~;
, j-, .... .
amine oxide; and the water-soluble sodium and potassium salts of ; :
higher fàtty acids containing 8 to 24 carbon atoms, and mixtures .
thereof respectively, and equivalent results are secured. ~.
In thè above composition the surfactant system is : :

replaced by an equivalent amount of a mLxture of alkyl ether :.

sulfate compounds compris~ng: from about 0.05%.to 5~ by weight of mixture of C12 13 compounds, from a~out 55% to 70% b~ weight '', ' -33- ; ~
.. i .

~04~5~2 of mixture of C14_15 compounds, from about 2.5~ to 40~ by weight of mixture of C16_17 compounds, from ahout 0.1% to 5% by weight of mixture of C18 19 compounds, from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of mixture Oe compounds having a degree of ethoxylation from 1 to 4, from about 12% to 22% by weight of mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0.5% to 10% by we:ight of mixture of compounds having a degxee of ethoxylation greater than 8, and 0 equivalent results are secured.
In the above composition the sodium sulfate is replaced by an equivalent amount of sodium carbonate, sodium bicarbonate, .
sodium silicate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, and the polymeric carboxylates set forth .in U.S. Patent 3,308,067, and mixtures thereof, respectively, and effective hard water detergenc~ is secured.
EXAMPLE V
A soap-based laundry granule is prepared having the following composition:
Component ~t.%
Sodium (1) soap 42.6 Potassium soap (1) 11.2 TAE3S(2) 10,7 Cll 8LAS(3) 8.8 Sodium silicate 8.9 Sodium citrate llo 9 Brightener 0.57 Perfume 0.17 Water 3.4 Miscellaneous Balance (1~ Soap mixtures comprising 90% tallow and 10% coconut soaps ~2) Sod~um salt of ethoxylated tallow al~yl sul~ate haY~ng ~4~5~2 an average of about 3 ethylene oxide units per molecule.

(3) Sodium salt of linear alkyl benzene sulfonate having an average alkyl chain length of a~out 12 carbon atoms. -~
Seventy-five parts by weight of the soap-based granules prepared above are admixed with 25 parts by ~weight of the amor-phous aluminosilicate prepared as disclosed in Example Io The composition is employed at 0.12% by weight of laundering liquor and provides excellent fabric cleansing and sudsing pxoperties in water having 10 gr/gallon mixed hardness~

The composition of Example V is modified by the addi-tion of 3 parts by weight of sodium perborate and excellent hot water (120F. - 180F.) cleaning performance is secured.
In addition to the foregoing, it has been found that the use of polyethylene glycols in the molecular weight range of from about 400 to about 8000, preferably about 6000, in the detergent compositions herein provides additional whiteness maintenance benefits. Polyethylene glycols are taught for use in detergents in U.S. Patent 2,806,001. The use of such materials at a concentration of from about 0.1-~ to about 3%, preferably 0.5~ to 1.5%, by weight of any of the foregoing detergent compo- `
sitions provides the desirable whiteness benefits. The following example illustrates a preferred detergent composition containing ' polyethylene glycol.
EXAMPLE VI
Component ~t %
.
Surfactant System comprising: 24.7%
Sodium linear alkyl benzene sulfonate wherein the alkyl group averages 11.8 carbon atoms in length 20% wt. ratio _ anionic/
Condensation product nonionic =
of one mole of coconut 4.26:1 fatty alcohol with about

6 moles of ethylene ;:
oxide 4.7%

: : . , ~
.

EXAMPLE VI con't.
Component Wt~%
*Aluminosilicate 42.0 Sodium silicate (Na O/SiO wt.
ratio = 1:2.4)2 2 15.0 Polyethyleneglycol (M.W. 6000~ 1.5%
Sodium sulfate 10.0 Sodium toluene sulfonate 2.0%
Water and minors Balance *Prepared as disclosed in Example I, hereinabove.
The foregoing composition is used to launder fabrics at a concentration of 1 cup/17 gal. water. The composition exhibits good fabric cleansing and superior whiteness maintenance in water of 7 gr.~gal. mixed hardness.
As can be seen by the foregoing, the amorphous alumino-silicate ion exchange builder materials herein can be employed in all manner of detergency compositions. The fact that the aluminosilicates are inorganic presumably accounts for their stability and compatibility with all manner of ingredlents employed in detergent compositions. Depending upon the desires ~' of the user, it is, of course, useful to add the aluminosilicate builder materials herein to a laundry or rinse liquor separately from the detergent compositions. Such separate use provides flexibility in the selection of the detergent composition employed by the user while providing the desirable benefits of the builder materials herein. Alternatively, the aluminosilicates herein can be employed in standard water softener appliances to pre-soften laundry water. Separate use of the aluminosilicate builders herein to pre-soften laundry water is fully contemplated by this invention.
T~e highly ~esirable speed and ion exchange capacity of the amorphous aluminosilicate materials herein is readily ~36-.

- - ~æ~so2 recognized when such materials are used to preso~ten laundry liquors. To be suita~le for such use, the aluminosilicate materials must not be so slow as to require an extensive waiting period prior to addition of a laundry detergent composition to the laundering liquor. ~oreover, it is likewise undesirable to require the user to utilize materials of such low ion exchange capacity that an unduly large quantity is required to effectively sequester hardness ions. Finally, it is desirable that the materials sequester mixed polyvalent hardness cations, such as ~ -Ca , Mg , Fe and Fe The amorphous aluminosilicate builders herein are ~ ~
useful in all manner of cleaning compositions. In ad~ition to ~ ~ -the foregoing, they can be effectively used in detergent-containing floor cleansers, scouring cleansers and the like, wherein water hardness also presents detergenay problems. Typical scouring cleansers can comprise, for example, from about 25% to about 95%
by weight of an abrasive (e.g., silica), from about 10% to about 35~ by weight of an amorphous aluminosilicate builder as disclosed herein, from about 0% to about 20% by weight of an auxiliary builder as disclosed herein, and from about 0.2% to about 10% by weight of an organic detergent compound.
Excellent cleaning performance is secured when mixed amorphous-crystalline aluminosilicates are used to replace the amorphous aluminosilicates of Examples II through VI.
Mixed amorphous-crystalline aluminosilicates are prepared in the manner disclosed in Example I without separation -of the amorphous and crystalline forms. Typical average crystal particle size is in the range of 5 to 12 microns.
, ' "' ,

Claims (15)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A detergent composition capable of rapidly reducing the free polyvalent metal ion content of an aqueous solution, comprising:
(a) from about 5% to about 95% by weight of an amorphous, water-insoluble, hydrated aluminosili-cate ion exchange builder material of the empirical formula Nax(xAlo2 .SiO2) wherein x is a number from 1.0 to 1.2 said builder material characterized by a Mg++
exchange capacity of at least about 50 mg eq.
CaCO3/g., and a Ca++ exchange capacity of at least about 200 mg eq. CaCO3/g.; and (b) from 0% to about 76% of a water-insoluble, crystal-line aluminosilicate ion exchange material of the formula Na12(AlO2 .SiO2)12.xH2O
wherein x is an integer of from about 20 to about 30, said crystalline aluminosilicate ion exchange material being characterized by a particle size of from about 1 micron to about 100 microns in diameter, a calcium ion exchange capacity which is at least about 200 mg equivalent of CaCO3 hardness/-gram of aluminosilicate, and further characterized by a calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram of alumino-silicate, said crystalline aluminosilicate not exceeding a weight ratio of 4:1 relative to the level of amorphous aluminosilicate; and (c) from about 5% to about 95% by weight of a water-soluble organic detergent compound selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic detergents, and mixtures thereof.

2. A composition according to Claim 1 wherein the amorphous aluminosilicate ion exchange material is further char-acterized by a Mg++ exchange rate of at least about 1 gr./gal./-min./g. and a Ca++ exchange rate of at least about 2 gr./gal./-min./g.

3. A composition according to Claim 1 wherein the detergent compound is a water-soluble salt of an organic sulfuric reaction product having in its molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group.

4. A composition according to Claim 1 wherein the detergent compound is a water-soluble soap.

5. A composition according to Claim 1 wherein the water-soluble organic detergent compound is selected from the group consisting of sodium linear C10-Cl8 alkyl benzene sulfonate; triethanolamine C10-C18 alkyl benzene sulfonate;
sodium tallow alkyl sulfate; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with from about 3 to about 10 moles of ethylene oxide; the condensation product of a coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide;3-(N,N-dimethyl-N-coconutalkylammonio)--2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkyl-ammonio)-propane sulfonate; 6-(N-dodecylbenzyl-N,N-dimethyl-ammonio)hexanoate; dodecyl dimethyl amine oxide; coconut alkyl dimethyl amine oxide; the water-soluble sodium and potassium salts of higher fatty acids containing 8 to 24 carbon atoms;
and mixtures thereof.

6. A composition according to Claim 1 wherein the water-soluble organic detergent compound is a mixture of alkyl ether sulfate compounds, comprising: from about 0.05% to 5% by weight of mixture of C12-13 compounds, from about 55% to 70% by weight of mixture of C14-15 compounds, from about 25% to 40% by weight of mixture of C16-17 compounds, from about 0.1% to 5% by weight of mixture of C18-19 compounds, from about 15% to 25% by weight of the mixture of the compounds having a degree of ethoxy-lation of 0, from about 50% to 65% by weight of the mixture of the compounds having a degree of ethoxylation from 1 to 4, from about 12% to 22% by weight of the mixture of the compounds having a degree of ethoxylation from 5 to 8 and from about 0.5% to 10% by weight of the mixture of the compounds having a degree of ethoxy-lation greater than 8.

7. A composition according to Claim 1 wherein the water-soluble organic detergent compound is a mixture of .alpha.-olefin sulfonates, consisting essentially of: from about 30% to about 70% by weight of a Component A, from about 20% to about 70% by weight of a Component B, and from about 2% to about 15% of a Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-1-sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5%
to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the func-tional units being hydroxy and sulfonate groups with the sulfonate groups always being on the terminal carbon and the hydroxyl group being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy group substitutions being in 3, 4 and 5 positions; and (c) said Component C is a mixture comprising from about 30%-95% water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70%
water-soluble salts of hydroxy disulfonates con-taining from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate group attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

8. A composition according to Claim 1, containing, as an additional component, from about 5% to about 50% by weight of an auxiliary, water-soluble detergency builder.

9. A composition according to Claim B wherein the auxiliary builder is selected from the group consisting of sodium tripolyphosphate and potassium tripolyphosphate.

10. A composition according to Claim 8 wherein the auxiliary builder is a non-phosphorus containing builder.

11. A composition according to Claim 10 wherein the auxiliary builder is selected from the group consisting of water-soluble inorganic carbonate, bicarbonate, and silicate salts.

12. A composition according to Claim 10 wherein the auxiliary builder is selected from the group consisting of water-soluble organic polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates.

13. A composition according to Claim 10 wherein the auxiliary builder is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesconate, sodium polyfumarate, sodium polyaconitate, sodium polycitraconate, sodium polymethylenemalonate, sodium carboxymethylmalonate, sodium carboxymethyloxysuccinate, sodium cis-cyclohexanehexacarboxylate, cis-cyclopentanetetra-carboxylate and sodium phloroglucinol trisulfonate.

14. A composition according to Claim 1 containing as an additional component from about 0.1% to about 3% by weight of a polyethylene glycol of a molecular weight in the range of 400 to 8000.

15. A composition according to Claim 14 containing from 0.5% to 1.5% of polyethylene glycol of a molecular weight of 6000.