CA1052221A - Detergent composition - Google Patents

Abstract

DETERGENT COMPOSITION
John Michael Corkill Bryan L. Madison Michael E. Burns ABSTRACT OF THE DISCLOSURE
Detergent compositions containing aluminosilicate ion exchange materials as builders are provided by one aspect of the invention as disclosed. The aluminosilicate builders are characterized by the speed and efficiency with which they remove hardness ions from water.
The invention in another aspect, resides in a water softener composition which comprises:
a) from about 5% to about 95% by weight of a water-insoluble crystalline inorganic aluminosilicate ion exchange material of the formula Na12 (AlO2?SiO2)12?x H2O
wherein x is an integer of from about 20 to about 30, said ion exchange material being characterized by a particle diameter of from about 1 micron to about 100 microns, a calcium ion exchange capacity on an anhydrous basis of at least about 200 mg eg./g, and a calcium ion exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute/gram; and b) from about 5% to about 95% by weight of an auxiliary builder.

Description

lOS'~Z~
BACKGROUND OF THE INVENTION
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 fabric-~c 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 effectively remove them from interaction with the fabrics and detergent materials in the laundering liquor. However, the use of such water- soluble builders necessarily introduces 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 compositions without the need for soluble builder additivé`s is desirable.
A 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 removed 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 example, Rao, in Soap Vol. 3 #3 pp. 3-13 (1950); Schwarz, et al. "Surface Active Agents and Detergents", Vol. 2, p. 297 et seq. (1966).
The zeolites, especially the naturally-occurring aluminosilicate

-2-~s~zz~
zeolites, have been suggested for use in washing compositions; see UO SO
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; 461,013; 462,591; and 522~ 097O
From the foregoing it is seen that a variety of methods have been heretofore employed to remove hardness cations from aqueous laundering ~ ~
systems concurrently with the deterging cycle of a home laundry operation. -However, these methods have not met with general success, primarily due to the inability of the art-disclosed materials to rapidly and efficiently reduce the free polyvalent metal ion content of the aqueous laundering liquor to acceptable hardness levelsO To be truly useful in laundry detergent compositions, an ion exchange material must have sufficient cation exchange capacity to significantly decrease the hardness of the laundry bath without requiring excessive amounts of the ion exchanger. Moreover, the ion exchange material must act rapidly, io e., it must reduce the cation hardness in an aqueous laundry bath to an acceptable level within the 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 calcium hardness to about 1 to Z grains per gallon within the ~-first 1 to 3 minutes of the deterging cycle. Finally, useful 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 aluminosilicate materials have both the high ion exchange capacity and the rapid ion exchange rate needed for cation exchange builder materials in laundry detergent -~
compositions.
Accordingly, it is an object of the present invention to provide detergent compositions containing insoluble, inorganic aluminosilicate ion exchange materials.
It is a further object herein to provide methods for laundering

- 3 _ ~os~z~z~
fabrics using the aforesaid detergent compositions.
These and other objects are obtained herein as will be seen from the following disclosure.
SUMMARY OF THE INVENTION
The instant invention is, in part, based on the discovery that cleaning and washing compositions capable of rapidly reducing the free polyvalent metal ion content in laundering liquor can now be prepared comprising a particular water-insoluble aluminosilicate ion exchange material in combination with surface active ingredientsO In particular, the detergent compositions of this invention comprise:
(a) from about 5% to about 95% by weight of a water-insoluble crystalline aluminosilicate ion exchange material of the formula Naz [ (A 1 O2) z . ( SiO2 )y ]XH2 wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, preferably from about 0.8 to 1.0; and x is an integer from about 15 to about 264, preferably about 27; said aluminosilicate ion exchange material having a particle size diameter from about 0.1 micron to about 100 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 mg. eq. /g.; and a calcium ion exchange rate on an anhydrous basis of at least about 2 grains/gallon/n~inute/gram;
and (b) from about 5% to about 95% by weight of a water-soluble organic surface-active agent selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surface-active agents and mixtures thereof.
The above compositions are disclosed and claimed in Canadian Patent Application 199,507, filed May 10, 1974, of which this application is a divisional.
In another embodiment, as clai~:ned in the present application,

- 4 -105'~;~Z~
the invention resides in a water softener composition comprising:
a) from about 5% to about 95% by weight of a water-insoluble crystalline inorganic aluminosilicate ion exchange material : -of the formula ~ ~.
Nal2(Al02.sio2)l2-~ H20 wherein x is an integer of from about 20 to about 30, said ion exchange material being characterized by a particle ~ :~
diameter of from about 1 micron to about 100 microns, a ~.
calcium ion exchange capacity on an anhydrous basis of at least about 200 mg eq. /g, and a calcium ion exchange rate :
on an anhydrous basis of at least about 2 grains/gallon/
minute /gram; and b) froIn about 5% to abouS 95% by weight of an auxiliary builder.
In a preferred embodiment herein, the water-insoluble ~ ::
aluminosilicate ion exchange material has the formula ~ .
Na 12 (A1O2 . SiO2 )12 .x H2 - :
wherein x is an integer of from about 20 to about 30 (preferably about 27)~
The detergent compositions herein can contain, in addition to the ion exchange material and organic detergent compound, various other 20 ingredients commonly ;, " ', .

_ 5_ 6 . .

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employed in detergent compositions. In particular, auxiliary, water-soluble builders can be employed in the compositions to aid in the removal of calcium hardness and to sequester magnesium cations in water where dissolved magnesi~m salts create significant hardness problems.
Additionally, the compositions herein can contain pH adjusting agents to ~aintain the pH of the laundering liauor within a desired range.

. 10 DETAIT.F~D DESCRIPTION OF l~lE INVENTION
The aluminosilicate ion exchange materials herein are prepared by a pro_ess which results in the formation of materials which are particularly suitable for use as detergency builders and water softeners.
Specifically, the aluminosilicates herein have both a higher calcium ion exchange capacity and a higher exchange rate than similar mater~als heretofore suggested as detergency builders. Such highjcalcium ion exchange rate and capacity appear to be a function of several interrelated factors which result from the method of preparing said aluminosilicate ion exchange materials.
One essential feature o~ the ion exchange builder materials herein is that they be in the "sodium form".
That is to say, it has surprisingly been found, for example, that the potassium and hydrogen forms of the instant aluminosilicate exhibit neither the exchange rate nor '.he exchange capacity necessary for optimal builder use, 105'~

~ second e~sential feature of the ion exchange builder material~ herein ~s that they be in a hydrated form, i.e. contain 10%-28~/o~ preferably 10%-22%~ by weight of water. Highly preferred aluminosilicates herein contain from about 18~ to about 22% (wt~) water in their crystal matrix.
It has been found, for example, that less highly hydrated aluminosilicates, 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.
A third essential feature of the ion exchange builder materials herein is their particle slze range Proper selection of small particle sizes results in fast, highly efficient builder materials.
The method set forth below for preparing the aluminosilicates herein takes into consideration all of the foregoing essential elements. Fir~t, the method avo~ds contamina~ion of the aluminosilicate product by cations other than sodiu~. For example, product washing steps involving acids or bases other than sodium hydroxide are avoided. 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 gr~nding operations can be employed to st~ll further reduce the particle size.

, 8_ ~ . . . . : : . -lOS'~ZZl ' However, the need for such mechanical reduction steps is sub~tantially lessened by the procesQ herein.
The aluminosilicates herein are prepared according to the following procedure:
(a) dissolve qodium aluminate (Na A102) in water to form a homogeneous solution having a concentration of Na A~O2 of - about 16.5% by weight (preferred);
~) add sodium hydroxide to the sodium aluminate solution of step (a) at a we~ght ratio of NaOH:Na AlO2 of 1:1.8 (preferred) and maintain the temperature of the solution at about 50~C until all the NaOH dissolves and a homogeneous ~olution forms;
(c) add sodium silicate (Na2 SiO3 having a SiO2:Na2O weight ratio of 3.2 to 1) to the solution of step (b) to provide a sol~tion having a weight ratio of Na2SiO3:NaOH of 1.14:1 and a weight ratio of Na2SiO3:NaAlO2 of 0.63:1;
(d) heat the mixture prepared in step (c~
to about 90C - 100C and maintain at this temperature range for about one hour.

In a preferred embodiment, the mixture of step (c~ i~ cooled to a temperature below about 25C, preferably in the range from 17C to 23~C, and main-t~ned at that temperatur~ for a period from about 25 hours to about S00 hours, preferably from about 75 hours to about 200 hours.

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Tne mixture resulting from step (d) is cooled to a temperature of about 50C and thereafter filtered to collect tne desired aluminosilicate solids. If the low temperature (<25C) crystallization technique is used, then the precipitate is filtered without addi-tional preparatory steps. The filter cake can option-ally be washed free of excess base (deionized water wash preferred to avoid cation contamination). The filter cake is dried to a moisture content of 18~ - 22%
by weight using a temperature below about 150C to avoid excessive dehydration. Preferably, the drying is performed at 100C - 105~C.
Following is a typical pilot-plant scale - -preparation of the aluminosilicates herein.

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The sodium alumin~te was dissolved in the water with stirr~ng and the sodium hydroxide added thereto.
The temperature of the mixture was maintained at 50C
and the sodium silicate was added thereto with stirring.
The temperature of the mixture was raised to 90C - 100C
and maintained wi~hin this range for 1 hour with stirring to allow formation of Nal2(AlO2-SiO2)12 27 H20. The mixture was cooled to 50C, filtered, and the filter cake washed twice with 100 lbs. of deionized water.
The cake was dried at a temperature of 100C - 105C to a moisture content of 18~/o ~ 22% by weight to provide the aluminosilicate builder material.
The aluminosilicates prepared in the foregoing manner are characterized by a cubic crystal structure.
Water-insoluble aluminosilicates having a molzr ratio of (A102):(SiO2) smaller than 1, i.e. in between 1.0 and about 0.5, can be prepared in a similar manner.
These aluminosilicate ion exchange materials (A102:SiO2 ~1) are also capable of effectively reducing the free polyvalent hardness metal ion content of an aqueous washing liquor in a manner substantially similar to the aluminosilicate ion exchange material having a molar ratio of AlO2:SlO,2 = 1 as described hereinbefore. Examples of aluminosilicates having a -molar ratio. A102:SiO2 Cli suitable for use in the instant compositions include:

, 1~)5~

86 [ (A12 ) 86 (Sio2 ) 106 ] ' 264 H2O; and Na6 [ (A 12 ) 6 (S io2 ) 10 ] ' 15 H2 .

:~os~z21 , Although completely hydrated aluminosilicate ion exchange materials are preferred herein, it is recognized that the partially dehydrated aluminosilicates having the general formula given hereinbefore are also excel-S lently suitable for rapidly and effectiveiy reducing the water hardnes~ during the laundering operation.
Of course, in the process of preparing the instant aluminosilicate ion exchange material, reaction- -crystallization parameter fluctuations can result in such partially hydrated materials. As pointed out previously, aluminosilicates having about 6% or less water do not ~unction effectively for.the intended ..
purpose in a laundering context. The suitability of .
particular..partially dehydrated water-insoluble 15 aluminosilicates for use in the compositions of this invention can easily be asserted and does only involve routine testing as, for example, described herein (Ca-ion exchange capacity; rate of exchange).
The ion exchange properties of the alumino-silicates herein can conveniently be determined bymeans of a calcium ion electrode. In this technique, the rate and capacity of Ca uptake from an aqueous solution containing a known quantity of Ca+~ ion is determined as a function of the amount of alumino-silicate ion exchange material added to the solution.
The water-insoluble, inorganic aluminosilicate ion exchange materials prepared in the foregoing manner are characterized by a particle size diameter from l~)S'~ZZl a~out ~.1 micron to about 100 microns. Preferred iron exchange materials have a particle size diameter from about 0.2 micron to about 10 microns. Additional preferred water-insoluble alumino-silicates herein are characterized by a particle size aiameter from about 0.2 micron to about 0.7 micron ~ The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determin-ation, scanning electron microscope (SEM).
The aluminosilicate ion exchangers herein are further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaCO3 hardness/gram of aluminosilicate, calculated-on ~n anhydrous basis, and which generally lies within the range of from about 300 mg. eq./g. to about 352 mg. eq./g.
The ion exchange materials herein are still further characterized by their calcium ion exchange rate, which is at least about 2 grains (Ca+~)/gallon/minute/gram of aluminosilicate lanhydrous basis), and lies within the range of about 2 grains/
gallon/minute/gram to about 6 grains/gallon/minute/gram, based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a Ca~ exchange rate of at least about 4 grainsJgallon/minute/gram.
The foregoing procedure for preparing the aluminosilicate ion exchange materials herein can ~e modified in its various process steps, as follows. -: - . : .

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Step (a) can be modified by u~ing solution concentra-tions of NaAlO2 of from 5% to 22% by weight; the optimum concentration is 16% to 16.5%. Step (b) can be modified by aeletion of the NaOH. Sodium hydroxide is no~ required to form the aluminosilicates herein but its use is preferred to initiate the reaction and to maintain reaction efficiency. Step (b~ can be further modified by use of temperatures within the range of from about 30C to about 100C; 50C is preferred. Step (c) can be modified by varying the ratio of aluminate to silicate. In order to satisfy - the 1:1 A102:SiO2 stoichiometry requirements of a specifically preferred species in the final product, it is necessary to provide in that particular case at 15 least a 1:1 mole ratio of AlO2:SiO2 (based on NaAlO2 and Na2SiO3) in t.ie mix. In ti~at latter event, it is highly preferred to employ an excess of NaAlO2, inasmuch as excess NaAlO2 has been found to promote the rate and efficiency of the formation reaction of aluminosilicates having a 1:1 molar ratio of AlO2:SiO2. Suitable water-insoluble aluminosilicate ion exchange materials having a molar ratio of AlO2:SiO2 of less than about 1.0, i.e. from 1.0 to about 0.5, can be prepared as described hereinbefore except that the molar amount of SiO2 is increased ~he proper determination of the excess silicate to be used in the formation reaction can easily be optimized and does only require a routine investigation.

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Step (d~ can be modified to employ temper-~tures from 50C to 110C at ambient pressure~, 90C to 100C is optimal. Of course, higher temperature~
can be employed if high pressure equipment i~ used to prepare the alum~nosilicates. When the high-temperature ~90-100C) crystalliz~tion technique i~ used, step (d) will normally require a formation reaction time of about 1 to 3 hour~. As noted hereinbefore, an addi-tional po~sibility for preparing the ion exchange materials resides in modifying step ~d) by cooling the mixture of step (c) to a temperature below about 25C, preferably in the range from 17C-23C, and maintaining said mixture at that temperature for a period from about 25 hour~ to 500 hours, preferably from about 75 hours to about 200 hours.
Following the formation of the aluminosilicates by the foregoing procedure, the materials are recovered and dried. When employed as ion exchange builders, th~
aluminosilicates must be in a highly hydrated form, i.e. 10% to 28%, preferably 10% to 22%, by weight of water. Accordingly, drying of the aluminosilicates must be carried out under controlled temperature condi-tions. Drying temperatures of from about 90C to about 175~C can be employed. However, at drying ~ -temperatures from about 150C to about 175C, the less highly hydrate~ materials (ca. 10% H20) are obtained. Accordingly, it is preferred to dry the alumlnosllicates at 100C to 105C, whereby the optimum "

.

` 105~'~Zl builder materials containing 18% to 22% by weight of water are securedO
At these latter temperatures, the stability of the preferred Z7-hydrate form of the aluminosilicate is independent of drying timeO
The ion exchange materials prepared in the foregoing manner can be employed in laundering liquors at levels of from about 0. 005% to about 0O 25% by weight of the liquor, and reduce the hardness level, particularly calcium hardness, to a range of about 1 to 3 grains/gallon within about 1 to about 3 minutes. Of course, the usage level will depend on the original hardness of the water and the desires of the userO Highly 10 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 compoundO
In another highly preferred embodiment, the compositions herein comprise from about 10% to about 50% by weight of the aluminosilicate builder.
DETERGENT COMPONENT
The detergent compositions of the instant invention can contain all manner of organic, water-soluble detergent compounds, inasmuch as the aluminosilicate ion exchangers are compatible with all such materials.
A typical listing of the classes and species of detergent compounds useful 20 herein appears in U, S. Patent 3, 664, 961 of Russell Norris, issued May 23, 1972. The following list of detergent compounds and mixtures which ~;
can be used in the instant compositions is representative of such materials, but is not intended to be limitingO

.

lOS~Z'~

~ater-soluble salts of t~e higher fatty acids, i.e. ~soapsn, are useful as the detergent component of the compositions herein. This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of Aigher fatty 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 saponifi-cation 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.

Another class of detergents includes water-solu~le salts, particularly the alkali metal, amm~nium 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. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic ~etergents ~hich 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 - C
carbon atoms) produced by reducing the glycerides of tallow or coconut oil; ana sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, .

e.g. those of the type described in United States Patents 2,22~,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 containing about 1 to about 10 units of ethylene oxideper 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 the polyoxyalkylene group which is condensed _ with any particular hydrophobic group ca~ be readily adjusted to yield a water-soluble compo~nd having the desired degree_s~ -balance between hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthe.tic detergents is made avai-lable on the market under the trade~
mark of "~luronic.'~ These compounds are formea by condensing - ~

lOSZ;~Zl ethylene oxide with a hydrophobic base formPd by the condensa-tion of propylene oxide with propylene glycolO Other suitable nonionic synthetic detergents include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of

5 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 wate~-soluble condensation products of aliphatic alcohols having 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 S to 30 mnles of ethylene oxide per mole of coconut alcohol, the 15 coconut alcohol fraction having from 10 to 14 carbon atoms,are also useful nonionic detergents herein.
Seml-polar nonionic detergents include water-soluble amine oxides containing one alXyl moiety of from about 10 to - :~
28 carbon atoms and 2 moieties selected from the group 20 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 from t~e group consisting of alkyl groups and hydroxyalkyl groups containing from 25 about 1 to 3 carbon atoms; and water-soluble sulfoxiae ~-.
.. ..

105~ZZ~
aetergents containing one alXyl iety of from about 10 to 28 carbon atoms and a moiety selected from the group consisting of alXyl and hydroxyalkyl moieties of from 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 c~ain or branched ana 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 compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic sub-stituents contains from about 8 to 18 car~on atoms and one contains an anionic water solubilizing group.
Other useful detergent compounds herein include thewater-soluble salts of esters of a-sulfonated fatty acids con-taining from about 6 to 20 carbon atoms in the fatty acid group 20 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 25 alkyl group and from about 1 to 30 moles of ethylene oxide;

-2a_ .

105~Z~ , ` .

- w~ter-soluble salts ~f olefin sulfonates containing from about 12 to 24 carbon atOmS; and ~-alkyloxy alkane sulfonates con-taining from about 1 to 3 carbon atoms in the alXyl 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 cont~ ns from about 14 to 18 carbon atoms and wherein the average degree of ethoxylation varies between 1 and 6; the `.
~ulfated 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; alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms, alXyldimethyl-ammonio-propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy-propane-sulfonates wherein the alkyl group in both types contains from about 14 to 18 car~on atoms: soaps, as hereinabove defined; the condensation :
product of tallow fatty alcohol wi~h about 11 moles of e.thylene oxide; and the condensation product of a C13 (avg.) secondary -alcohol with 9 moles of ethylene oxide.

. Specific preferred detergents for use herein include: sodiu~ linear C10 - C18 alkyl benzene sulfonate;
triethanolamine C10 - C18 alkyl benzene sulfonate: sodium '~'. ' .
. ............... . . ~ . ~ .............. . . . .
' ' ' '' ~ . . : ,, , 105~
tallow alkyl sulfate; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated con~ensation product -~ of a tallow alcohol with from about 3 to about lO moles of ethylene oxide~ the condensation product of a coconut fatty alcohol with about 6 m~les of ethylene oxide; the condensation product of tallow fatty alcohol with about ll moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio).-2-hydroxypropane-l-sulfonate; 3-(N,~-dimethyl-N-coconutalkylammonio-propane-l-sulfonate; 6-(N-dodecylbenzyl-N,~-dimethylammonio)hexanoate; :~
10 dodecyl dimethyl amine oxide; 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 e reoognized that any of the foregoing ~ .
detergents can be used separately herein or as mixtures.
15 Examples of preferred detergent mLxtures 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 lS carbon atoms, and :
an average (arith~etic mean) degree of ethoxylation of from . about 1 to 4 moles of ethylene ~xide, preferably from about 2 to 3 moles of ethylene oxide.
J . ---.25 __ ~ , , , . . - . ' ., '~

~ ,. . . .

Specifically, such preferred mixtures comprise from about 0.05% to 5% by weight of mixture of C12 13 compounds, from about 55% to 7~/O by weight of mixture of C14 15 compounds, from about 25% to 4~O by weight of mixture of C16 17 compounds and from about 0.1% to 5% by weight of mixture 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 ethoxylation from 1 to 4, from about 12% to 22% by weigh~ of mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0.5% to l~/o by weight of mixture of compounds having a degree of ethoxylation 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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H
~ . . .-. . ,', ~ ' Ed dP , tlP
~H CO dP dP d~ dP 11'3 0~ --I 0 1~ H ~ '1 ~1 . t~ 7 t~l O Z
H ~ ~o ~ . t~ ~ ~1 . , _ 12 0~ ~
~ ~ W dP d~ ~ ~ dP ~
:~: H ~ ~ ~ . _1 ~ 1` ~ Z
E l ~ ~D r~ N ~ 11'1 _I
. E" _l H --~ . ' ~ ~ ~D dP d~ d~ dP OD dP dP dP dP
E~ :~; H 'r ~ U-) ~ ~ '~ ~
. ~S _l U~ _l ~ `J ., _ ~ ~
. , dP dP -dP J~ J~
~ 3 3 3 _ __ ~ ~. 3 _ dP dP dP dP ~1 _ ~ a .... x ~a ~ a) O ~ 1 H 3 . 3 3 :~c .C ^ ~ X X -~
E~ C:^ _ j_ _ _ ~ 0 ~1 O O X
tl~ -~ U~ . ~ ~:1 X O
H ~ ~ tr~ O C) O
~ s O ~ ~
E~ ~ o, 1 0 0 0 O CJ au a) CJ
El ~C ~: !~ ~ IJ _I ' ~
~> ~ I~ ~U Oa~
~ O U ~ ~ ~
P~ .~:a ~ ~ ~ ~ ~ s ~ ~ o o o o ~ ~ a) a~
:~ ~ o ~ ~ 5~ ~ . g) o ~ a o o z ~ ~ z a) L~ ~0 _ ~ _ ~ .
w a) ~ .) a) u~
tr: ~ ~ ~ ~ O O _~
::) ~ ~ ~ ~ O ~ O
E- h b~ ~1 ~ I ~rl O E~
X Q~ ~ I I ~ I I ~ ~ ~
H ~ 0 t~ ~ ~D 0 ~ 0 I I ~ 1~
~: ''S-:l ~ 1 ~ O ~ 1~ O~ ~a U~ O U~

- ` .
105i~Z2~L
- Preferred "olefin sulfonate" detergent mixtures utilizable herein comprise olefin sulfonates containing from a~ou~ 10 to about 24 carbon atoms. Such m~terials can be produced by sulfonation of Q-olefins by means of uncomplexed sulfur dioxide followed by neutralization under conditions.
such that any sultones present are hydrolyzed to the corres-ponding hydroxy-alXane sulfonates. The a-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred ~-olefin sulfonates are described in U. S. Patent ;
3,332,880 of Ressler et al., issuea July 25, 1967.
., , ~, ~ Preferred ~-olefin sulfonate mixtures-herein consist essentially offrom about 30/O to about 7~/O by weight of a Component A, from about 2~/o to about 70/O by weight of a Component B, and from about 2% to about 15% of a Component C, 15 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 10 to about 24 carbon atoms, said mixture of positional isomers including about l~/o to about 25% of an alpha-beta unsaturated isomer, about 30/O to about 70/O of a beta-gamma unsaturated isomer, about 5~O to about 25% of gamma-delta unsaturated isomer, and about 5% to about l~/o of a delta-epsilon unsaturated :~.

l~S'~Z'~l 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 functional units being hydroxy - .- ana sulfonate groups with the sulfonate ;~
groups always being on the terminal - - ;
carbon and the hydroxyl group being attached to a carbon atom at least tw~ carbon atoms removed.from the terminal carbon atoms at least 90/O of the hydroxy ~roup substitutions being in 3, 4, and 5 positions; and ~c) said Component C is a mixture.comprising from about 30/O-95% water-soluble salts of alkene . disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 7~% water-soluble salts of hydroxy disulfonates containing from about 10 to about Z4 carbon atoms, said alkene disulfonates containing a sulfon.ate 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 2~ carbon atom,.the alkene double bond being dis-tributea between the terminal carbon atom and -- .

b t th lU~ h~l ' 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 ~erminal 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.

. ~OS'~Z21 Auxiliarv Builders A~ noted hereinabove, the detergent composition3 of the present invention can contain,in addition to the aluminosilicate ion exchange builders, auxiliary,water-soluble builders such as those taught for use in detergent compositions. Such auxiliary builders can be employed to aid in the seguestration of hardneqq ionq and are particularly useful in combination with the aluminosilicate ion exchange builaers in qituations where magnesium ions contribute significantly to w~ter hardness. Such auxiliary buil~erq can be employed in concentrations of from 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 activity 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, orthophosphates, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates. Specific examples ~f inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates, phosphates, ana hexametaphosphates. The polyphosphonates specif-ically include, for example, the sodium and potassium salts of ethylene aiphosphonic acid, the sodium and potassium salts ofethane l-hydroxy~ diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of _30_ 1~)5'~ZZl these and other phosphorus builder compounds are disclosed in U.S. Patents 3,-159,~81,--3,213,030, 3,422,021, 3,422,137"
` 3,400,176 and 3,400,148.
~ on-phosphorus containing .~equestrants can also bc selected for use herein as auxiliary builders.
Specific examples of non--phosphorus, inorganic auxi- ;
liary aetergent builder ingredients include water-soluble inorganic carbonate, bicarbonate, ana silicate saltq. The al~ali metal, e.g., soaium ana pota~-3ium, carbonate , bicarbonates, and silicates are particularly useful herein.
Water-soluble, organic auxiliary builders are also u~eful herein. For example, the alXali metal, ammonium ~;
and substituted ammonium polyacetateY, carboxylates, --polycarboxylates and polyhydroxysulfonates are useful auxiliary :
builders in the present compositions. Specific example~
of the polyacetate and polycarboxylate builder sa~ts - -include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic a~id nitril~triacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
Highly preferred non-phosp~orus auxiliary builder ~ . materials herein include sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, soaium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, and sodium ethylenediaminetetraacetate, and-mixtures thereof.
Other highly preferred auxiliary builders herein are the polycarboxylate builders set forth in U.S. Patent 3,30~,067, -- 105'~

Diehl, issued March 7, 1967. Examples of such material~ include the water-soluble salts of homo- and co-polymerq of aliphatic carboxylic acidq such as m~leic acid, itaconic acid, meqaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid, 1,1,2,2-ethane tetracarboxylic acid, dihydroxy tartaric acid and keto~malonic acid.
Additional, preferred auxiliary builders herein include the water-qoluble saltq, especially the ~odium and potasqium ~altq, of carboxymethyloxymalonate; carboxymethyl-oxysuccinate, cis-cyclohexanehexacarboxylate, ciq-cyclopenta-netetracarboxylate and phloroglucinol tri~ulfonate.
Specific examples of highly preferred phosphorus con-taining auxiliary builder salts for use herein include alkali pyrophosphates whereby the weight ratio of ion exchange material to pyrophosphate is within the range from about 1:2 to about 2:1. Additional preferred auxiliary co-builders such as the alkali salts of sodium tripolyphosphates and nitrilotriacetic acid provide equally superior performance for a weight ratio of ion exchange material to`,auxiliary builder salt in the range from about 1:1 to abdut 1:3.
The ion exchange aluminosilicates in combination with citrate auxiliary builder salts will provide superior free metal ion depletion in washing li~uor when the zeolites used have a 25 molar ratio of AlO2:SiO2 of 1:1. It is understood that in the above preferred ranges of auxiliary builder to alumino-silicate the builder component can be represented~by mixtures of said builders.
The detergent compositions herein containing the aluminosilicate ion exchange builder and the auxiliary, water-_32-, 105~2~1 soluble builder are useful by virtue of the fact that the aluminosilicate preferentially adsorbs calcium ion in the presence of the auxiliary builder material. Accordingly, the calcium hardness ions are primarily removed from solu-tion by the aluminosilicate while the auxiliary builderremains free to sequester other polyvalent hardness ions, such as magnesium and iron ions.
The deter~ent compositions herein can contain all manner of a~ditional materials commonly found in laundering 10 and cleaning compositions. For example, such compositions can contain thickeners and soil suspending agents such as carboxymethylcellulose and the like; Enzymes, especially the proteolytic and lipolytic enzyme~ commonly used in laundry d~tergent compositions,can also be present herein.
15 Various perfumes, optical bleacheQ, filler~, anti-caking agent3, fabric softeners and the like can be present in the compositions to provide the usual benefits occasioned by the use of such materials in detergent composition~. It is to be recognized that all such adjuvant materials are 20 useful herein inasmuch as tney are compatible and stable - -in the presence of the aluminosilicate ion exchange builders.

The granular detergent compositions herein can also advantageously contain a peroxy bleaching component in an 25 amount from about 3% to about 40% by weight, preferably from about 8% to about 33~ by weight. Examples of suitable peroxy bleach components for use herein include perborates, l(~S;~2Z~

persulfates, persilicates, perphosphates, percarbonates and more in general all inorganic and organic peroxy bleaching agents which are known to be adapted for use in the subject compositions.
The detergent compo~itions o this invention can be prepared by any of the several well known procedures for preparing commercial detergent compositions. For example, the compositions can be prepared by simply admixing the alumin~ilicate ion exchange material with the water--soluble organic detergent compound. The adjuvant builder material and optional ingredient~ can be simply admixed therewit~, as desired. Alternatively, an aqueous slurry of the aluminosilicate on exchange ~ilder containing the dissolved, water-soluble organic detergent compound and the optional 15 and auxiliary materials can be spray-dried in a tower to provide a granular composition. The granules of such spray-dried detergent compositions contain the alumino-~ilicate ion exchange builder, the organic detergent compound and the optional and auxiliary materials.
Alternatively, the aluminasilicate ion exc~ange materials herein can be employed-separately in aqueous laundry and/or rinse baths to reduce hardneQ~ cations. When . 80 employed, the user can simply admix an effective amount, i.e., an amount sufficient to lower the hardness 25 to about 1 to 2 grains per gallon, to the aqueGus bath ana thereafter add any commercial detergent compo~ition -~

105'~ZZ~ , of choice. Generally, when employed in this manner the aluminosilicate will be added at a rate of about 0 005% to about 0.25h by weight of the aqueous bath.
The ion exchange alumino~ilicates herein can also 5 be employed in combination with standard cationic fabric ~ofteners in fabric rinses. When so employed, the alumino-silicates remove the hardnes~ cations and result in a softer feel on the softened fabrics Typical cationic fabric softeners useful in combination with the alumin~silicate 10 ion exchangers include tallowtrimethylammonium ~romide, tallowtrimethylammonium chloride, ditallowdimethylammonium bromide, ana ditallowdimethylammonium chloride. Aqueous fabric softener compositions containing the aluminOsilicate ion exchangers comprise from about 5~O to about 95%
15 by weight of the aluminosilicate and from about 1%
to about 35% by weight of the cationic fabric softener.
~ he detergent compositions herein are employed in a~ueous liguors to cleanse surfaces, especially fabric surfaces, using any of the standard laundering and cleansing 20 techniques. For example, the compositions hérein are particularly suit~d for use in standard automatic washing machines at concentrations of rom about 0.01% to about 0.50% by weight. Optimal results are obtained when the compositions herein are employed in an aqueous lzundry 25 bath at a level of at least about 0.10% by weight. As _ ~ 35 lOS;~2;~1 in the case of most commercial laundry detergent composi-tion~, the dry compo-qitions herein are usually added to a conve~tional aqueous laundry solution at a rate of about 1.0 cup/17 gallons of wash water.
While the aluminosilicate ion exchange builder materialq herein function to remove calcium hardness ions over a wide pH range, it ix preferred that detergent compositions containing such materials have a pH in the range of from about 8.0 to about 11, preferably about 9.5 10 to about 10.2. As in the case of other standard deterge~
compositions, the compositions herein function optimally within the basic pH range to remove soils and triglyceride solls and -~tains. While the aluminosilicate~ herein inherently provide a baqic solution, the detergent compo-sitions comprising the aluminosilicate and the organicdetergent compound can additionally contain from about 5% to about 25% by weight of a pH adjusting agent. Such compositions can, of cour~e, contain the auxiliary builder materials and optional ingredients aq hereinbefore ae-qcribed The pH adjusting agent used in such compositions are--selected such that the pH of a 0.05/0 by weight aqueous mixture of--said compo~ition iq in the range of from about 9.5 to about 10.2.

. .

-~)5~
The optional pH adjusting agent~ u~eful herein include any o~ the water-solu~le, basic m~terials commonly employed in detergent compositions. Typical examples of such water-soluble materials include the sodium phosphates; sodium silicates, especially those having a silicon dioxidP:sodium oxide weight ratio of from akout 1:1 to about 1:3.2, preferably from about 1:1.7-to about L:2.3; sodium hydroxide:
pota~sium hydroxide; triethanolamine; diethanolamine;
ammonium hydroxide and the like. Preferred pH adjusting 10 agents herein include sodium hydroxide, triethanolamine and sodium ilicate.
The following examples are typical of the detergent compositions herFin, but are not intended to be limiting thereof.

(~ :

.

... ' 105~
o ~ .
J~ , ~, .
~q , o u 3 t~l 'r e~ ~ . . .
O
_~ ~ a~ , O ~ ,.~
- , ,.. :
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O ~ ' :.,' ~1 -rl ~ U ` U
:~ ~ U~
O

~ ~ O ~
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dP d -~1 x ~n a~ ~r a) :
W
O
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.
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_38_ :
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.

S;~Z;~l ` The foregoing composition provides excellent fabric laundering performance when employed under conventional home laundering conditions in a laundering liquor-of 7 grains gallon hardness with a composition concentration in the laundering liquor of about 0.12% by weight. Under such conditions sudsing and cleansing performance of the Example I composition compares favorably with that of conventional, fully built, high-sudsing anionic detergent formulations. Such a composition-is pourable and is prepared with conventional spray-drying apparatus.
Compositions of substantially similar performance quality are secured when, in the above-desçribed Example I composition, the sodium tallow alkyl sulfate is replaced with an equivalent amount of potassium tallow alkyl sulfate, sodium coçonut 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-~enzene sulfonate potassium undecyl benzene sulfonate,-potassium tridecyl-benzene sulfonate, potassium tetradecyl benzene sulfonate and potassium tetrapropylene benzene sulfonate, respectI~ely.
Compositions of substantially similar performance quality, physical characteristics and processability are secured ~:
when in the above-described Example I composition, the conaensation ;~
product of the 15 carbon atom secondary ~ 39 -105~
alcohol with 9 moleq 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 conden~ation product of coconut fatty alcohol with about 6 moles of ethylene oxide (HLB = 12.0); "Neoa~ol 23-6.5n* (HLB = 12); "Neodol 25-9"** (HLB = 13.1); and "Tergitol 15-S-9~*** (HLB = 13.3), respectively.

* Trademark ** Trademark *** Trademark :~ ( l(~5;~

EX~MPLE II

A spray-dried detergent composition useful in water containing both Ca~ and Mg++ hardness is prepared having the following composition:

. Wt.%
Component 24 7% . ~' Surfactant system comprising:
Sodium linear alkyl benzene sulfonate wherein the alkyl group averages about 11.8 carbon atoms in length Condensation product ( anionic/
o one mole of coco- ~ nonionic =
nut fatty alcohol 4 26 1 with about 6 moles of ethylene oxide . -~5.0%
*Nal2~AlO2 sio2~12 27 2 15.0 Sodiùm silicate (Na~O/SiO2 ~t. ratio = 1:2.4 20.0%
Sodium citrate 5.0 . Sodium Acetate 2.0%
Sodium toluene sulfonate . 4.0 Water Balance Minors *prepared in the mdninemreter 7.5 microns ~I~

105'~Z2~
The composition of Example II provides excellent fabric cleansing performance when employed under conventional home laundering conditions in a laundering liquor of 7 grains/gallon mixed Ca+fand Mg++
hardness with a composition concentration in said laundering liquor of about 0. lZ% by weightO The composition pH in solution is caO 10.2 at this concentrationO Under such conditions, sudsing performance of the : -Example II composition compares favorably with that of conventional, fully-built, high-sudsing anionic detergent formulationsO Such a composition is readily pourable and storage stable and is prepared with conventional spray-drying apparatusO
Compositions of substantially similar performance quality, physical characteristics and processability are secured when, in the above composition, the sodium citrate is replaced by an equivalent amount of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium ~:
silicate, sodium oxydisuccinate, sodium mellitate, sodium nitrilo-triacetate, sodium ethylenediaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconitate, sodium polycitraconate, sodium polymethylene-malonate, and mixtures thereof, respectivelyO
A composition of substantially similar performance quality, physical characteristics and processability is - 42 - :

. . :. .

securea when, in the above described Example II compo~i-tion, there i9 incorporated about 3% by weight of ~odium perborate solid~ with all other components remaining in ~he same relative proportions. Such perborate composi-tions are particularly adapted for u~e under the wa~hingconditions 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 IV appearing in Table I, respectively, and excellent detergency performance is secured.
In the above composition the Nal2(A102 SiO2)12-27H20 is replaced with Nal2(A10? SiO2)12 2 Nal2(A12'SiO2)12'30H20, respectively, and equivalent re~ults are secured.

( -105;~

EXAMPLE III

A phosphorus-free detergent composition is prepared having the following composition:
.

Component . Wt.%
-*Surfactant System . 35%
Triethanolamine (pH-adjusting 7% .
agent) :
NaO~ (p~-adjusting agentj . 0.5%
**Nal2(AlO2-sio2)l2 27 ~2 Sodium Citrate 15~
Water and Minors Balance -.
:, .
*The Surfactant System comprises an ~-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-so.luble salts of alkene-l-sulfonic acids con- -. :
taining from about 10 to about 24 carbon atoms, said ~ixture 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 un-saturated 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 CarDOn atoms, the functional units being hydroxy and sulfonate groups with the sulfonate groups ~ .
always being on the terminal carbon and the . -hydroxyl group being attacned to a carbon atom at least two carbon atoms removed from the terminal car~on atoms, at least 90% of the nydroxy group su~stitutions being in 3, 4, ana 5 positions; and ~ .

-4 ~
. .

~()5~

(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 from about 10 to about 24 car,bon 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 seventn carbon atom, '-said hydroxy disulfonates'being saturated aliphatic compounds having a sulfonate group attached to a terminal carbon, a second sulfonate group attacned 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.
**Prepared as disclosed hereinabove. Average particle diameter 12 microns.

~OS~,ZZl The composition of Example III is added to an aqueous bath at 110F at a rate of 0.15% by weight and used to launder oily fabrics. Excellent cleaning results are secured under initiai 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 - 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 ethy-lene oxide; the condensation product of tallow fatty alcohol with about 11 m~les of ethylene oxide; 3-~N,N-dimethyl-N-coconutalkylam~onio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkyla D nio-propane-l-sulfonate 6-(N-dodecyl-benzyl-N,N-dimethyla D nio)hexanoate; dodecyl dimethyl amine oxide; coconut alkyl dimethyl amine oxide; and the water-soluble sodium and potassium salts-of higher fatty acids containing 8 to 24 carbon atoms, and mixtures thereof, respectively, and equivalent resul~s are secured.
In the above composition the Surfactant System ~s replaced by an equivalent am~unt of 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 7~ by weight of mixture of C14 15 compounds, from about 25% to 4~0 by weight o~ mixture of C16 17 compounds, from about 0.1% to 5% by weight .~ .

__ _ . _ - \ ~
~ 05' '`'~1 of mixture of C18 19 compounds from a~ut 15~ to 25% by w~ight of mixture of compounds ha~ing a degree of ethoxylation of ~, from about 5~O to 65% by weight of mixture of eompounds hav;.ng ~`a degree of ethoxylation from 1 to 4, from about l~/o to 22% by weight of mixture of compounds having a degree of ethoxylation from S to 8 an~ from about 0.5% to l~o by ~eight of mixture of eompounds having a degree of ethoxylation greater than 8, and equivalent results are secured.
In the above composition the sodium citrate is replaced by an equivalent amount of sodium carbonate, sodium bicarbonate, sodium silicate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, and the polymerie car-boxylates set forth in U.S. Patent 3,308,067, and mixtures thereof, respectively, and effective hard water detergeney is secured.
- In the above composition the sodium eitrate is suecessiYely replaced by an equivalent amount of the sodium and potassium salts of carboxymethyloxymalonate, carboxymethyloxysuccinate, eis-cyclohexanehexacarboxylate, eis-cyclopentanetetraearboxyl-ate and phloroglucinol trisulfonate, respectively ande~fective hard water detergency is secured.

( . .
10~
EXAMPLE IV

A soap-based laundry granule is prepared having the following composition:

- Component Wt.
Sodium soap(l) 42.6 Potassium soap(l) 11.2 TAE3S( ) 10.7 Cll 8LAS(3) 8.8 Sodium silicate 8.9 Sodium~citrate 11.9 Brightener 0.57 Perfume - 0.17 Water 3.4~~ -Miscellaneous Balance .
(1) Soap mixtures comprising 90% tallow an~ 10%
coconut soaps.
(2) Sodium salt of etnoxylated tallow alkyl sulfate having an average of about 3 etnylene oxide units per molecule.
(3) Sodium salt of linear alkyl benzene sulfonate having an average alkyl chain length of about 12 carbon atoms.

( Seventy-five partS by weight of the soap-based granules prepared above are admixed with 25 parts by 12( 12 SiO2)12 27H20 (prepared in the manner disclosed hereinabove; 25 micron size). The compo-sition is employed at 0.12% of weight of laundering liquor and , provides excellent fabric cleanqing and sudqing propertiesin 10 gr/gallon hard water.
The composition of Example IV is modified by the addition of.3 part~ by weight of sodium perborate and excellent hot water (12~F. - 180F.) cleaning performance is secured.

( -\
l~S~ZZ~ ' A~ can be seen by the foregoing, the aluminosilicate ion exchange builaer materials herein can be employed in all m~nner of aetergency compositions. Moreover, the aluminosilicate builders in combination with water-soluble auxiliary builder~ which sequester magnesium, iron and other polyvalent water hardnesq cations can also be em~ oyed in comb~nation with all manner of detergent compositions. Depending upon the desires of the user, it is, of course, useful to add the alumino~ilicate builder or aluminosilicate-plus-auxiliary builder materials to a laundry or rinse liquor separately from the detergent compositions.
Such separate use provides flexibility in the selection of the deter-gent compo~ition employed by the uSOE while providing the d~sirable benefits of the builder materials herein. Separate use of the aluminosilicate builders and aluminosilicate-plus-auxiliary builder compositions herein to soften water are fully con-templated by this invention.
Inasmuch as most hard water contains polyvalent m~tal ions in addition to caicium ions, the use of the aluminosilicate builders as water softeners is preferably -carried out i~ the presence of an auxiliary builder of thetype hereinbefore disclosed. Such auxiliary builders can be any of the phosphorus-containing builders, or, in regions where such builaers are unacceptable, any of the hereinabove disclose~
non-phosphorus builder materials. The aluminosilicate builders and the auxiliary builaers can, of course, be separately aAded to water to exert their softening function. However, it is more convenient to add such materials simultaneously to the water _50-1.05'~2Zl ~o be treated. Accordingly, there are provided to the user compositions comprislng from about 5% to about 95% by weight of the aluminosilicate builder materials herein, and from a~out 5 ~ to about 95 % by weight of an auxiliary builder of the type hereinabove disclosed. Preferably, such -compositions wqll contain a weight ratio of.aluminosilicate builder:auxiliary builder of from about 5:1 to about 1:5_ Such compositions can be provided to the user in any of the physical forms convenient for u~e as laundry builders, such as dry powders, tablets, pre-measured . packets, or in water-soluble packages which can simply be added to the aqueous so~ution to be softened. Various adjunct material-~ ~uch as bleache~, bluing, fabric softeners, sud~ control agent~, perfumes, sanitizers and the like can be optionally incorporated into such compositions to provide desirable additional benefit.~
. . The highly desirable speed and ion exchange capacity of the aluminosilicate materials herein is readily recognized when such materials are used to presoften laundry liquors.

To be suitable for such use, the materials must not be so_.
slow as to require an extensive waiting period prior $o addition of a laundry detergent composition to the laundering liquor. Moreover, it is likewise undesirable to require the user to utilize material~ of such l~w ion exchange quantity that an unduly large qua-ntity is required to effectively -_ sequester hardness ions. For these reasons,.the aluminosilicates herein are particularly adapted for such bu~der ana water-softening purposes.

-5~-l(~S~

The following is an example of a builder composition of this invention which is suitable for use in water containing all ma~ner of polyvalent hardness cations.

1~)5~

EXAMPLE V

Component Wt.%
.
*Nal2(Al02 SiO2)12 27 H2 Sodium Citrate 50 *Prepared as described herein.
Partlcle diameter 100 micr~ns.

~OS~Z~:l The above composition is provided as a granular powder. The pow~er is adaed at a rate of 2 oz. per 20 gallons of wash water and agitated for V2-minute. During -this time, haraness cations are su~stantially reduced to a level of about 1 - 2 gr/gal (starting with 7 grain/gallon hard water). A
comm~rcial laundry detergent composition is thereafter adde~
to the aqueous bath. Fabrics laundered in such pre-softened water are more effectively cleansed than in water which has not been pre-softened.

In the above compositiOn, the Nal2(A102 SiO2)12 27H20 i~ replaced by an equivalent amount of Nal2(A1~2-SiO2)12 20H20 and ~al2(A12 SiO2)12 30H2o, prepared as disclosed herein, respectively, and equivalent results are secured.
In the above composition the sodium citrate is replaced 1~ by an ~quivalent amount of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium oxydisuccinate, sodium mellitate~ sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconitate, sodium polycitraconate, sodium poly-methylenemalonate, sodium carboxymethyloxymalonate, sodium carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, and mixtures thereof, respectively, and cffective hard water dctergency is securcd.
The foregoing compositions are employed at concentrations of 0.005% to 0.25% by weight and effectively softcn water containing polyvalent cations.

The aluminosilicate builderq and alumino~ilicate-plus~
auxiliary builder mixtur~s h~rcin are useful in all mann~r of cleaning compo~ition~. In addition to the foregoing, they can be effectively used in detergent-containing floor clean~ers, scouring cleansers and the like, wherein water hardness also presents detergency problem~. Typical scouring clean~ers can comprise, for example, from about 25% to about 95% by weight of an abraYive (e.g., silica), from about 10% to about 35% by weight of an aluminosilicate builder aq 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.

10~

. EXAMPLE VI

A detergent base granule having the following composition was prepared by conventional spray-drying.
, Ingredient . Parts by Weight .
(1~ ' .
TAE3S 14.5 Sodium tallow alkyl sulfate 2.5 Silicate solids 13.0 ~ratio: Na20/SiO2 = 2.0) Sodium sulfate 15.0 Minor ingredients including 5.0 sodium toluene sulfonate, trisodium sulfosuccinate, moisture, etc.

(1) Sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide units per molecule.

105;~ZZl .
A mixture was then prepared containing the above detergent base granule and a builder component listed hereinafter in the proportions specified. The composi-tion so obtained was used for cleaning polyester F
swatches which had been stained with a clay soiling composition. To tnat end, the swatches were laundered - for ten minutes at 105F in a laundering liquor con-taining 0.12% by weight of the above detergent composition. i The hardness and calcium-magnesium ratio were varied as indicated. After being laundered, tihe swatches were rinsed, removed from the washer and dried. The cleaning performance was expressed as a summation of Hunter Whiteness readings for 0, 2, 4, 6, 8, 10 and 12 grains hardness/gallon (Ca/Mg = 2/1) whereby the Hunter Whiteness equals 0 when 0.06~ by weight sodium sulfate is used instead of .he builder mixture and equals 100 when 0.06%
;~ by weight sodium tripolyphosphate is used as builder component. The 0.06% replacement level relates to the amount of said inqredients in the laundering liquor.

The builder component was represented by a mixture of an aluminosilicate having the formula Nal2(AlO2 sio2)12 27 ~2 prepared as described hereinbefore and having an average particle diarleter of 3 microns and an auxiliary builder selected from sodium pyropnosphate, sodium tripoly-phosphate, sodium nitrilo-triacetate and sodium citrate.
The base detergent granule represented 0.06% by weignt of the laundering liquor; the remaining 0.06% by , ' ' . , - \

weight was represented by a builder component as indicated.
The whiteness resuits were:

. ~ .

. Sodium Hunter Aluminosilicate~l) Pyrophosphate(lj Whiteness 0.02 o.b4 117 0.03 0.03 102 0.04 0.02 . g4 (1) in % by weight of laundering liquor.

~05'~ZZl Sodium citrate was evaluated as auxiliary builder in lieu of sodium pyrophosphate thereby using the testing conditions set forth. In addition, the Ca/Mg hardness level was varie~ as indicated. Tne Hunter Whiteness readings were as foll~ws:

- - , ::

~ ~, Sodium Hunter Ca:Mg Aluminosilicate(l) citrate(l) Whiteness . :
1:1 0.04 0.02 35 . 0.03 0.03 61 0.02 0.04 51 ::
.
2:1 0.04 0.02 38 . 0.03 0.03 52 . , 0.02 ~.04 53 J
' 3:1 0.04 0.02 37 0.03 0.03 54 0.02 ; 0.~4 50 .

~ (1) In ~ by weight of laundering liquor.

, ' : ':.

--5 ~

10~'~2'~ .
The sodium salt of nitrilotriacetic acid and sodium tripolyphosphate were also evaluated as auxiliary builders in substitution for the sodium pyrophosphate builder thereby using the testing conditions set forth above. The Ca:Mg ratio was 2:1. The Hunter ~niteness readings were as follows: .

Alumino- Sodium-nitrilo Sodium tri- Bunter silicate(l) triacetate(l) Polyphosphate(l) Whiteness .
., . .
L 0.02 0.04 108 0.03 0.03 82 0.04 0.02 . 64 0.02 : . . 0.04 95 0.03 0.03 91 0.04 . 0.02 -79 (1) In % by weight of laundering liquor.

lOS'~

The foregoing testing data hiyhlight the superior cleaning perormallce derived from the use of specific combinations of aluminosilicates and auxiliary builder salts in detergent context.
Compositions capable of providing substantially similar performance are obtained when the sodium salt .
of.the ethoxylated tallow alkyl sulfate is substituted by a substantially equivalent amount of sodium tallow alkyl sulfate, sodium coconut alkyl sulfate and sodium decyl benzene sulfonate.
Substantially similar results are also obtained when the Nal2(A12-Si2)12'27 H2O is replaced with an equivalent amount of Nal2(AlO2-SiO2)12-20 H2O;
l~a (AlO SiO2)12 30 H2O~ Na861(A12)86( 2 106 2 and Na6[(AlO2)6(SiO2)10]-15 H2O, respectively.

~)S;~

EXAMPLE VII

A granular detergent composition is provided having the following composition:

InqredientParts by Weight TAE3S( ) - 14.~
Sodium tallow alkyl sulfate2.1 Sodium tripolyphosphate 24.0 Nal2(AlO2~sio2~l2 27 2 18.0 Sodium sulfate ~ 36.6 Brightener 0.9 Moisture 5.0 (1) Sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide u~its per molecule.
(2) Prepared as described herein. Average particle size diameter 3-5 microns.
.

~ A

lOS;~

The above composition is capable of securing excellent soil removal and cleaning performance during conventional laundering when using water naving a high initial water hardness, for example from 7 to 14 grains per gallon of Ca/Mg nardness.

Claims (15)

The Embodiments of the Invention in Which an Exclusive Property or Privilege is Claimed are Defined as Follows:

1. A water softener composition comprising:
a) from about 5% to about 95% by weight of a water-insoluble crystalline inorganic aluminosilicate ion exchange material of the formula Na12 (AlO2?SiO2)12? x H2O

wherein x is an integer of from about 20 to about 30, said ion exchange material being characterized by a particle diameter of from about 1 micron to about 100 microns, a calcium ion exchange capacity on an anhydrous basis of at least about 200 mg eq./g, and a calcium ion exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute/gram; and b) from about 5% to about 95% by weight of an auxiliary builder.

2. A composition according to Claim 1 wherein the aluminosilicate ion exchange material has a calcium ion exchange capacity on an anhydrous basis from about 200 to about 352 mg. eq./g., and a calcium ion exchange rate on an anhydrous basis of from about 2 to about 6 grains/gallon/minute/gram.

3. A composition according to Claim 1 wherein the aluminosilicate ion exchange material has a particle diameter from about 0.2 micron to about 0.7 micron.

4. A composition according to Claim 1 wherein the aluminosilicate ion exchange material has a particle diameter from about 0.2 micron to about 10 microns.

5. A composition according to Claim 1 wherein the aluminosilicate ion exchange material has a particle diameter from about 1 micron to about 10 microns.

6. A composition according to Claim 1 or Claim 2 wherein the aluminosilicate material is Na12 (AlO2 . SiO2)12 . 27H2O.

7. A composition according to Claim 3, 4 or 5 wherein the aluminosilicate material is Na12 (AlO2 . SiO2)12 . 27H2O.

8. A composition according to Claim 1 or Claim 2 wherein the auxiliary builder is selected from the group consisting of water-soluble phosphates, polyphosphates, carbonates, bicarbon-ates, silicates, carboxylates, polycarboxylates, polyhydroxysulfonates, and mixtures thereof.

9. A composition according to Claim 3, 4 or 5 wherein the auxiliary builder is selected from the group consisting of water-soluble phosphates, polyphosphates, carbonates, bicarbon-ates, silicates, carboxylates,polycarboxylates, polyhydroxysulfonates, and mixtures thereof.

10. A composition according to Claim 1 or Claim 2 wherein the auxiliary builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylene-diaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconi-tate, sodium polycitraconate, sodium polymethylenemalonate, sodium carboxymethyloxymalonate, sodium carboxymethyloxy-succinate, sodium cis-cyclohexanehexacarboxylate, sodium cis-cyclopentanetetracarboxylate and sodium phloroglucinol trisulfonate.

11. A composition according to Claim 3, 4 or 5 wherein the auxiliary builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylene-diaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconi-tate, sodium polycitraconate, sodium polymethylenemalonate, sodium carboxymethyloxymalonate, sodium carboxymethyloxy-succinate, sodium cis-cyclohexanehexacarboxylate, sodium cis-cyclopentanetetracarboxylate and sodium phloroglucinol trisulfonate.

12. A composition according to Claim 1 or Claim 2 wherein the weight ratio of aluminosilicate: auxiliary builder is from about 5:1 to about 1:5.

13. A composition according to Claim 3, 4 or 5 wherein the weight ratio of aluminosilicate: auxiliary builder is from about 5:1 to about 1:5.

14. A composition according to Claim 1 or 2 wherein the aluminosilicate material is Na12 (AlO2 ? SiO2)12 ? 27H2O, the auxiliary builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylene-diaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconi-tate, sodium polycitraconate, sodium polymethylenemalonate, sodium carboxymethyloxymalonate, sodium carboxymethyloxy-succinate, sodium cis-cyclohexanehexacarboxylate,sodium cis-cyclopentanetetracarboxylate and sodium phloroglucinol trisulfonate, and the weight ratio of aluminosilicate:
auxiliary builder is from about 5:1 to about 1:5.

15. A composition according to Claim 3, 4 or 5 wherein the aluminosilicate material is Na12 (AlO2 ? SiO2)12 ? 27H2O, the auxiliary builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylene-diaminetetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, sodium polyfumarate, sodium polyaconi-tate, sodium polycitraconate, sodium polymethylenemalonate, sodium carboxymethyloxymalonate, sodium carboxymethyloxy-succinate, sodium cis-cyclohexanehexacarboxylate, sodium cis-cyclopentanetetracarboxylate and sodium phloroglucinol trisulfonate, and the weight ratio of aluminosilicate:
auxiliary builder is from about 5:1 to about 1:5.