CA1058040A - Molecular sieve zeolite-built detergent paste - Google Patents

Abstract

ABSTRACT
Detergent pastes, containing a water-soluble synthetic organic detergent, a particulate molecular sieve zeolite in cation exchanging form and an aqueous medium, in certain proportions, are stable, homogenous detergents, possessing properties.

Description

58~
` MOLECULAR SIEVE ZEOLITE-BUILT DETERGENT PASTE
- :
i; This invention relates to aqueous paste detergent compositions.
-; More particularlyl it relates to such pastes which contain water insoluble molecular sieve zeolites.
,~ Some of the physical disadvantages of solid detergent compositions, such as particulate detergents, have resulted in a preference of some con-sumers for aqueous liquid detergents. Particulate detergents are often ~".. . -.
prepared by drying, e.g., spray drying, an a~ueous mixture of detergent ~ ingredients. During such drying volatile constituents of the detergent .~ , formulation may vaporize, resulting in serious atmospheric pollution and ~ economic loss. Liquid detergents require no substantial drying and their ,... .
preparation avoids this detriment. Furthermore, because of their fluidity, liquid detergents can be measured or metered out in required amounts in automatic washing operations with greater facility than solid detergents.
;~ However, a disadvantage of liquid detergents is the difficulty of preparing ' ~ a homogeneous liquid detergent containing a water-insoluble ingredient such : ~./ .
~ as an insoluble detergency builder. Attempts to disperse particulate, in-i;~ ;~ i ., .soluble components in a liquid detergent have often resulted in the eventual :',! settling out of the insoluble material. The resultant two-phase mixture may be rejected by consumers as unsightly despite the fact that the insoluble material may often be redispersed in the liquid by agitation or mild shaking.
:- Accordingly, the present invention provides a stable, homogeneous paste detergent composition comprising 5% to 50% by weight of a water-. soluble, synthetic organic detergent~ 5% to 60% by weight of a water-insoluble ' ~-~v molecular sieve aluminosilicate zeolite buildereffective to sequester calcium ;
; j ions selected from the group consisting of Type A,X,Y,L, mordenite and ~'' erionite, said zeolite being in the form of particles having a mean particle -~

diameter of from 0.5 to 12 microns, having a univalent cation selected from .; ,.. .
~ the group consisting of sodium, potassium, lithium, ammonium and hydrogen, ~
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30 and containing 1.5% to 36% by weight of water, and 10% to 70% by weight of an aqueous medium.
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Preferably, the novel paste detergent contains 15 to 35% by welght of the organic detergent, 20 to 35% of the water insoluble molecular ~'~ sieve zeolite and 25 to 50% of aqueous medium. Preferably also the :`,~!.', ' detergent paste contains 5 to 35%, preferably 8 to 20% of a water soluble ,.} builder.
, - The present invention also provides a method of washing laundry ~"`J~ ~
which comprises contacting it with an aqueous solution having a temperature ;~ from 10C to 90C and containing from .07 to 0.9% by weight of a stable n~ homogeneous paste detergent composition comprising 5% to 50% by weight of a .,.;. ~
10 water-soluble, synthetic organic detergent, 5% to 60% by weight of a water-insoluble molecular sieve aluminosilicate zeolite builder selected from the ~ .
group consisting of Type A,X,Y,L, mordenite and erionite, said zeolite being in the orm of cryst&lline particles having a mean particle diameter of from 0.5 to 12 mlcrons, having a cation selected from the group consisting ,, .:
of sodium potassium, lithium, ammonium and hydrogen, being effective to se-quester calcium ions and being in a hydrated form wherein 1.5% to 36% by weight ;: i of water is present, and 10% to 70% by weight of an aqueous medium.
;:.. 1 .
The novel paste of the invention can be made by combining the sur-factant, the zeolite molecular sieve and the aqueous medium and stirring, ~ 20 shaking or agitating the mixture for about 1 to 15 minutes, advantageously -i~ for about 1 to 5 minutes. Generally the agitation of the aqueous mixture can ~: be effected at a temperature in the range of 10 to 80C., preferably 10 to ..... , ~
:~; 50C but most preferably the mixing operation is carried out at about ambient L~ temperature~ e.g., 15 to 35C. Advantageously an electric blender, a dough ,!. j .:
mixer, a soap crutcher, a homogenizer or equivalent agitation device may be ~-~ used to prepare the paste.

The detergent paste of the invention is an aqueous fluid or gel ~,- wherein the insoluble molecular sieve is homogeneously dispersed. It may be :... ;, , in cake form and can be of a viscosity in the range from thin gel to thick 30 paste. The insoluble builder does not settle out to produce an unsightly sediment. Because of its capability of being extruded orllliquefied'' the :
~ paste can be metered o~: measured out in washing operations with a ,.:,

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facility comparable to that of prior art liquid detergents and hence may be referred to as "fluid". Additionally, the paste detergent is prepared without extensive drying or evaporation operations, thereby avoiding the pollution hazards and losses sometimes associated with the manufacture of i particulate detergents. Also, compared to the mixing of powders without drying, dusting is prevented.
The molecular sieves utilized in the invention are water insoluhle crystalline aluminosilicate zeolites of natural or synthetic origin which are characterized by having a network of uniformly sized pores in the range :: , O
of about 3 to 10 Angstroms, preferably about 4 A (nominal), which size is .~ uniquely determined by the unit structure of the zeolite crystal. Of course, zeolites containing two or more such networks of different size pores can also be employed.
The molecular sieve zeolite should also be univalent cation-exchang-ing zeolite, i.e., it should be an aluminosilicate of a univalent cation ; such as sodium, potassium, lithium, when practicable or other alkali metal, ammonium or hydrogen. Preferably, the univalent cation associated with the ; zeolite molecular sieve is an alkali metal cation, especially sodium or ....................................................................... . .
,:.- potassium. ~ ' ;, Crystalline types of zeolites utilizable as molecular sieves in ~`; the invention, include zeolites of the following crystal structure groups:
;,. . ~ .
~ A,X,Y,L, mordenite, and erionite. Mixtures of such molecularsieve zeolites .. .~. . .:.
can also be useful, especially when type A zeolite is present. These -~ p~eferred crystalline types of zeolites are well known in the art and are ; more particularly described in the text Zeolite Molecular Sieves by Donald ~`
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,-~ W. Breck, published in 1974 by John Wiley ~ Sons. Typical commerically ~. .................................................................... ;.
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a~ailable zeolites of the aforementioned structural types are listed in Table 9 a 6 at pages 747-749 of the Breck text.
Preferably the molecular sieve zeolite used in the invention is a synthethic molecular sieve zeolite. It is also preferable that it be of type A crystalline structure, more particularly described at page 133 of the aforementioned te~t.
An e~pecially good result is generally obtained in accordance with the invention when a Type 4A molecular sieve zeolite is employed, wherein the univalent ca~ion of the zeolite is sodium :
and the pore size of the zeolite is about 4 Angstroms. The expecially preferred zeolite molecular sieves are described in United States patent 2,882,243 which refers to them as Zeolite A.

Molecular sieve zeolites can be prepared in either a : .
dehydrated or calcined form which contains from less than about 1~5% to abaut 3% of moisture or in a hydrated or water loaded form which contains additional absorbed water in an amount up to about 36% of the zeolite total weight, depending on the type ~`~ of ~eolite used. Preferably, the water-containing hydrated form of the molecular sieve zeolite is employed in the practice of the invention. The manufacture of such crystals is well known ".,.~.
-` in the art, For example, in the preparation of Zeolite A ~ i referred to above, the hydrated zeolite crystals that are formed in the crystalli~ation medium (such as a hydrous amorphous sodium aluminisilicate gel) are used without the high temperature .",~
~- dehydration &calcining to 3% or less water content) that is . .. .

~ normally practiced in preparing such erystals for use as . .
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catalysts, e.g., cracking catalysts. The preferred form of zeolite in either completed hydrated or partially hydrated form can be recovered by filtering off the crystals from the crystallization medium and drying them -in air at ambient temperature so that their water content is in the range of about 20 to 28.5%, preferably about 20 to 22%.

The crystalline zeolites used as molecular sieves should also ... ,i ~ be substantially free of adsorbed gases, such as carbon dioxide, since such ;, , gas-containing zeolites can produce undesirable foaming when the zeolite-j: 1 - containing detergent is contacted with water; however, sometimes the foaming .. . . . .
is tolerated.
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; The molecular sieve zeolite should be in finely divided condition ; such as crystals tamorphours or poorly crystalline particles may also find some use) having mean particle diameters in the range of about 0.5 to about 12 microns preferably 5 to 9 microns and especially about 5.9 to 8.3 microns, : . . .
;~, mean particle size, e.g., 6.4 to 8.3 microns.

', The water soluble organic detergent which is employed in the !;. ' ~i detergent paste can be selected from any of the principal classes of such `

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detergents, i.e., it can be selected from anionic, nonionic, cationic and ~" amphoteric detergents. These categories of water soluble synthetic organic detergents are more particularly described in McCutcheon's Detergents and Emulsifiers, 1969 Annual and by Schwatrz, Perry and Berch in Surface Active .,.~ ~,. ..
~gents, Vol. II ~Int~erscience Publishers, 1958).

Suitable anionic water soluble surfactants include higher ~10 to ,~ 20 or 12 to 18 carbon atom alkyl benzene sulfonate salts, preferably linear . alkyl benzene sulfonates wherein the alkyl group ,~.,, :
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contains lO to 16 carbon atoms. The alkyl group is preferably ` linear and especially preferred are those of average alkyl chain lengths of about ll to 13 or 14 carbon atoms~
Preferably also, the alkyl benzene sulfonate has a ; high content of 3- ~or higher) phenyl isomers and a correspond-ingly ~ow content ~well below 50%) of 2_ (or lower) phenyl - isomers; in other terminology, the ben~ene ring is preferably attached in large part at the 3 or higher (e.g., 4, 5, 6, or 7) position of the alkyl group and the content of isomers in which the ben~ene ring is attached at the 2 or l position is correspond-.:
~ inglysll~w.
. .
Also, typical of the useful anionic detergents are the olefin sulfonate salts. ~enerally, they contain long chain `
, ` , alkenyl sulfonates or long chain hydroxyalkane sulfonates (with the OH being on a carbon atom which is not directly attached : .
~ to the carbon atom bearing the -S03 group). More usually, the :;:
olefin sulfonate detergent comprises a ~xture of these two types of compo~nds in varying amounts, often together with long :;., ` chain disulfonates or sulfate-sulfonates. Such olefin sulfonates ;~ 20 are described in many patents and in the article by Baumann et al.

~` in Fette-Seifen-Anstrichmittel, Vol~ 72, No. 4, at pages 247-253 ~; (1970). As indicated in these patents and the .,.., : .-~, ...
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published literature~ the olefin sulfonates may be made from straight chain alpha-olefins, internal olefins, olefins in which the unsaturation ls in a vinylidene side chain (e.g~, dimers of alpha-ole~in), etc., or, more usually, mixtures of such compounds, with the alpha-olefin usually being the ma~or constituent. The sulfonation is usually carried out with sulfur trioxide under low partial pressure~ e.g., S03 highly diluted with inert gas such as air or nitrogen or under vacuum.
This reaction generally yields an alkenyl sulfonic acid, often together with a ~ultone. The resultlng acidic material is generally then made alkaline and treated to open the sultone ring to form hydroxyalkane sulfonate and alkenyl sul~onate. The number of carbon atoms in the olefin is usually within the range :;i . , .
; of 10 to 25, more commonly 12 to 20, e.gO, a mixture of pr ncipally C12' C14 and C16, having an average of about 14 carbon atoms or a mixture of principally C14, C16 and C18, ~; havlng an average of about 16 car~on atoms.
Another class of water soluble synthetlc organic anlonic ~.,; .
/~ detergents includes the higher (10 to 20 carbon atoms) paraffin sulfonates. The~e may be the prlmary paraffln sulfonates made by . .
reactlng long chain alphd-ole~in~ and biaulfite~ e.g~, sodium i bisul~lte, or paraffin sulfonates having the sulfonate groups distributed along the paraffin chain, such as the products made by reacting a long chain paraffin wlth sulfur dioxide and oxygen under ultravlolet light, ~ollowed by neutrallzation with NaOH or other ~uitable base.

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The hydrocarbon substituent of the paraffin sulfonate preferably contains 13 to 17 carbon atoms and the paraffin sulfonate will normally be a monosulfonate but, if desiredl may be a di-, tri-- or higher sulfonate. Typically, a paraffin disulfonate may be employed in admixture with the corresponding monosulfonate, for ~; example, as a mixture of mono- and di-sulfonates containing up to about 30~ of the disulfonate.
The hydrocarbon substituent of the paraffin sulfonate ~` will usually be linear but branched chain paraffin sulfonates `.' 10 can be also employed. The paraffin sulfonate used may be ~.............................................................. .
terminally sulfonated or the sulonate substituent may be joine~
to the 2-carbon or other carbon atom of the chain. Similarly, any di- or higher sulfonate employed may have the sulfonate groups distributed over different carbons of the hydrocarbon ~`;;; 15 chain.
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i Other anionic detergents that can be used are the ~ .; .
., ~ ., .
water soluble salts or soaps of, for example, such higher fatty carboxylic acids as lauric, myristic, stearic, oleic, elaidic, ~` isostearic~ palmitic, undecylenic, tridecylenic, pentadecylenic, .~...
~, 20 2-lower alkyl higher alkanoic (such as 2-methyl tridecanoic, 2-methyl pentadecanoic or 2-methyl heptadecanoic) or other ~-, saturated or unsaturated fatty acids of 10 to 20 carbon atoms, preferably of 12 to 18 carbon atoms. Soaps of dicarboxylic acids may also be used, such as the soaps of dimerized linoleic :; .
','r`' 2S acid. Soaps of such other higher molecular weight acids ;.`
as rosin or tall oil acids, e.g., abietic acid, may be employed.
One specific suitable soap is the soap of a mixture of tallow fatty acids and coconut oil fatty acids (e.g., in 85:15 ratio).
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For the purpose of this speciflcation the! soaps will be con~ldered in the class o~ synthetic detergents.
Other anionic detergents are sulfates o~ higher , ~. .
alcohols, such as sodium lauryl sulfate, sodium tallow alcohol sul~ate, sulfated oils9 or sulfates of mono- and diglycerides of higher fatty acids, e.g., stearic monoglyceride monosulfate;
higher alkyl polyethenoxy ether sulfates, i.e., the sulfates ~ . .
of the conden~ation products of ethylene oxide, and a higher `:
allphatic alcohol, eOg., lauryl alcohol, wherein the molar ~i 10 proportion of alkylene oxide to alcohol is from 1:1 to 5:15 ; lauryl or other higher alkyl glyceryl ether sulfonate~; aromatic pol~Yethenoxy ether sulfate~ such as the sulfates of the conden-~ation products of ethylene oxide and nonyl phenol (u~ually having 1 to 20 oxyethylene group~ per molecule and pre~erably, 1 15 2 to 12). The ether sulfa-te may also be one having a lower ,,i,. "
alkoxy (of 1 to 4 carbon atom~, e~.g., methoxy), s~bstituent on a carbon close to that carrylng the sulfate group, such as a mono~ethyl ether mono~ulfate o~ a long chain viclnal glycol~
~; e~g., a mixture of vlcinal alkane diols o~ 16 or 17 to 18 or 20 carbon atoms in a straight chain.
Additional wat~r ~oluble anionic surfactants in~ ude ,i ~- the higher acyl sarcosinates (e.g., sodium lauroyl sarcosinate) ~` the acyl esters, e.g~, oleic acid ester, of isethionate~ and ~; acyl N-meth~l tæurides, e.g., potas~ium N-methyl lauroyl- or oleyl taurides. Another type of anionic surfactant is a higher alkyl phenol ~ulfonate, ~or example, a higher alkyl phenol disulfonate, such as one having an alkyl group of 12 to 2~ carbon atomsg ,..~......
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preferably a linear alkyl of about 16 to 22 carbon atoms, which may be made by sulfonating the corresponding alkyl phenol to a product containing in excess of 1.6, preferably above 1.8, e.g~, to 1.9 or 1.95 SO3H groups per alkyl phenol molecule. The ,i ~;. 5 disulfonate may be one whose phenolic hydroxyl group is blocked, . . ,; .
as by etherification or esterification; thus the H of the phenolic OH may be replaced by an alkyl, e.g., ethyl or hydroxyalkoxy-alkyl, e.g., a -(CH2CH2O)XH group in which x is 1 or more, such ~ . . .
` as 3, 6 or 10,and the resulting alcoholic OH may be esterified to form, say, a sulfate, e.g., -SO3Na.

While the aforementioned structural types of organic `~ carboxylates, sulfates and sulfonates are generally preferred, ~ the corresponding organic phosphates and phosphonates are also. ~ .
useful as anionic detergents.

~r~, 15 Generally, the anionic detergents are salts of alkali ;~; metals, such as potassium and especially sodium, although salts '"!:' of ammonium cations and substituted ammonium cations derived from ;~I lower (2 to 4 carbon atoms) alkanolamines, e.g., triethanolamine, ~' tripropanolamine`, diethanol monopropanolamine, and from lower (1 ~, 20 to 4 carbon atoms) alkylamines, e.g., methylamine, ethylamine, ' ;."!
; ~ sec-butylamine, dimethylamine, tripropylamine and tri-isopropyl-` ' amine, may also be utilized.

Of the anionic detergents the alkali metal salts of sulfated and sulfonated oleophilic moieties are preferred over the carboxylic, phosphoric and phosphonic compounds.

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The nonionic sur~actant~ having the most desirable detergency properties are usually viscous liquids or unctuous, pa~ty or tacky solids at room temperature, such as those having melting polnts below about 40 C. and having significant volatlllty or fuming properties under conditlons, e.g., spray drying, used commerclally to dry particulate detergents. Typical nonionic ' . .
~ detergents are polyethenoxy derivatives that are usually , prepared by the condensation o~ ethylene oxide, to compounds having a hydrophobic hydrocarbon chain and containing one or more actlve hydrogen atoms, such as higher alkylphenols, ~ hlgher fatty alcohols, higher ~atty acids, higher fatty !" ;' mercaptans9 higher fatty ~mines, and higher ~atty polyols and . .. .
`: alcohols~ e.g., fatty alcohols having 8 to 20 carbon atoms in , ~
~ an al~l chaln and alkoxylated with an average o~ about 3 to i . ~

3 lower alkylene oxide units.
Preferred nonionic surfactants are tho~e represented ., ~ji; by the formula:

Ro(c~H4o)nH
;. . ~, , ... .
`i~ whereln R repre~ent~ the re~idue of a linear saturated primary :, -,~ . .
~; 20 alcohol (an alkyl) of 12 to 18 carbon atoms and n is an integer ~rom 6 to 20.
- Typlcal commercial nonionic sur~actants suitable for ~; u~e ln the invention include Neodol 45-11, which is an ethoxylation product (having an aver~ge of ll ethylene oxide ., . ~ ,~ . .

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units) ~ a 14 to 15 carbon atoln ch~lin f~ltty alcohol (Shell Chernical Company); Ncodol 25-7, a 12 to 15 carbon atom chaill fatty alcohol ethoxylated with an average of 7 ethylene oxide units; and Alfonic 1618-65, which is a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 ethylene oxide units ~Continental Oil Company). Also useful are the Igepals of GAF Co., Inc.
- Cationic organic surfactants include quaternary amines having a water soluble anion such as acetate, sulfate or chloride.
Suitable quaternary ammonium salts may be derived from a higher ~i fatty primary amine by condensation with a lower alkylene oxide '~ similar to that described above for preparation of nonionic surfactants. Typical cationic surfactants of this type include ~, Ethoduomeens~/12 and T/13, which are ethylene oxide condensates ~ 15 of N-tallow trimethylene diamine tArmour Industrial Chemical Co.) `I and Ethoquad la/12, 18/25 and 0/12 whieh are polyethoxylated ~'~` quaternary ammonium chlorides (Armour Industrial Chemical Co.).
: Cationic surfactants also include quaternary ammonium salts derived from heterocyclic aromatic ~mines such as Emcol E-607 which is N-(lauryl eolamino formyl methyl) pyridinium chloride . ... . .
,' (Witco Chemic~l Corp.). Also sometimes classified as cationic ,r surfactants are hiqher fatty amine oxides such as Aromox 1~/12 -~ which is bis(2-hydroxyethyl) octadecylamine oxide (Armour Industrial Cher~lical Co.).

Amphoteric organic surfactants are generally higher r fatty carboxylates, phosphates, sulfates or sulfonates which j;

~' - eontain a eation substituent such as an amino group which may .` ! :.
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be quatcrnized, for example, with a lower alkyl group, or may have the chain thereof extended at thc amino group by condensation ~;
i with a lower alkylene oxide, e.g., ethylene oxide. In some .
instances the amino group may be a member of a heterocyclic ring.
.
Representative commercial water soluble amphoteric organic ., detergents include Deriphat*151,which is sodium N-coco beta-.
aminopropionate (General Mills, Inc.) and Miranol C2M (anhydrous .i acid),which is the anhydrous form of the heterocyclic diamino-,. . .
~ dicarboxylic compound of the formula,,~ ' ~
,,` \
.!'r: ' , 11 ¦ ~ CH2CH20cH2cOoH ', `
j~`' 10 CllH23 ~-- CH2COOH

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The water soluble organic detergent employed in the detergent paste of the invention preferablv includes a nonionic surfactant and of the nonionics it is especially preferred to ,~ 15 employ a polyalkoxylated higher fatty alcohol of the formula -;~ previously presented. The detergent paste may preferàbly contain .~,;.; , several different types of water soluble detergents. For example, when the principal detergent is nonionic there is often desirably . present an anionic detergent, such as a sulfate or sulfonate,which ~ .
~ .
~ is in a proportion up to about 25~, e.g., 2 to 25%, preferably i~, -. about 5 to 12~, based on the weight of the paste. Use of a water :.
` soluble linear higher alkyl benzene sulfonate, such as the sodium ~
` salt, as the anionic detergent is especially preferred. In such ~`
combinations o anionic and nonionic detergents, especially when :,,; :~ .
;;;`i 25 the ratio of anionic:nonionic is in the range of 0.3 to 1 or 0.5 to 1, rather than less than 0.3, the presence of the anionic . ................................... .
detergent makes the product creamier, less likely to dry out on storage (6 months) and more effective in washing out mixed soils .;, . . .
~ on laundering.
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The solvent or fluid medium for the presen~ paste detergent is an aqueous one. It may be water alone or may be substantially water with additional solvents added to solubilize particular ingredients. Because of the availability of water ; 5 and its minimum cost, it lS preferred to use it as the sole solvent present. Yet, amounts of other solvents, usually in .,,~ , proportions from about 0 or 0.1 to 20%, preferably totaling about 5 to 15% of the detergent paste, may be present. Generally, i .~
,~ such a supplemental fluid or solvent is a lower aliphatic .. . .
~; 10 alcohol (including t he mono-, di- and polyhydric alcohols, such . , i as alkanols, diols and triols, as well as ether alcohols and '`, ~li polyols), e.g., methanol, ethanol, n-propanol, isopropanol, .~` n-butanol, ethylene glycol, propylene glycol, glycerol, diethylene .. . .
; ~ glycol. In this connection, ethanol is especially preferable.
The water utilized in preparing the present paste detergent may be tap water but is preferably deionized water.
The water insoluble molecular sieve zeolite present in ..: ..
` ~ the detergent pastes has an excellent building effect on the . ~, . .
detergency of the paste. However, the paste preferably also contains a water soluble builder salt or a mixture of such salts.
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`'`~ The water soluble builder salt may be either an organic or inorganic builder salt. Representative organic builder salts ~, include the water soluble, such as alkali metal and especially sodium salts of nitrilotriacetic acid, citric acid, 2-hydroxy-.; ".., ethylene iminodicarboxylic acid, boroglucoheptanoic acid, poly-` carboxylic acids, e.g., polymaleates of low molecular weight ;~ (generally below 1,000, e.g., 400, 600, or 800), and poly-. .. - . .
phosphonic acids. Normally one will prefer to avoid using phosphorus-containing compounds.
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~''',' ; Representative inorganic builders which may be incorporated in the paste with the molecular sleve zeolite, alone or in mixture, are water soluble silicates, e.g., alkali metal ..... .
~''` 5 silicates wherein the molar ratio of metal oxide to SiO2 is ` about 1:1.5 to 1:3.2, alkali metal polyphosphate salts, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate and ~.............. .
`~ alXali metal carbonates such as sodium carbonate.

The supplemental water soluble builder is preferably an , ............. .
inorganic salt and more preferably a non-phosphate builder, e.g., . a water soluble silicate. Particularly good results are obtained ~ with alkali metal siliçates such as so~ium silicate. Preferably, `;i the molar ratio of Na2O to SiO2 in the silicate builder is about 1:2 to 1:2.5.
The concentration o~ supplemental water soluble builder incorporated in the detergent paste according ~ a preferred embodi-~` ment of the invention is in the range of a~out 5 to 35% and is .. . .
~ preferably about 8 to 20%.
`~ The detergent paste of the invention may also advantage-ously include amount9 up to about 8~, say, for example, 0.01, 0.2, l, 3 and 5%, of conventional functional or aesthetic ad~u-vants, the total amount of such adjuvants not exceeding 20% ~0 ~..
~;`` to 20%), preferably 5 to 15%, e.g., 7 to 10%.

An especially important adjuvant which may be present ~" ` .
in the paste is an organic anti-redeposition agent such as alXali ;~ metal carboxymethyl cellulose, e.g., sodium carboxymethyl `; ~ cellulose, polyvinyl alcohol, hydroxymethyl ethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, hydroxypropyl ethyl . .. ;,.

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cellulose or mixtures thereof Preferably the gum anti-redeposi-tlon agent is sodium carboxymethyl cellulose, which is advantageously incorporated at a concentration of up to about ; 3%, such as 0 2 to 2~, preferably 0.2 to 0.5~.
;~ 5 Another typical class of minor adjuvants which may! be incorporated in the pa~te detergent are colorants, e.g.,`~ pigments, dyes and optical brighteners.
` The colorants used may be inorganic plgments such as ,. : .
Ultramarine Blue, organic pigment~ such as beta-chlorophyll or . , organic dye6 ~uch as Color Index Direct Blue 1.
The optical brighteners used are fluorescent dyes including coumarins, triazolyl stilbenes, stilbene cyanurics, acylamlno 3tilbenes or mi~cellaneous types such as shown in issued patents. The concentration of brightener is advanta-geou~ly in the range of about 0.05~ to 1~, e.g., 1/10% to 1/2%.
One ~uitable combination of brighteners includes a naphthotriazole stilbene sulfonate brightener, sodlum 2-sulfo-4 (2-naphtho-1,2~
l .
;`~!, triazol~l) stllbene; another stilbene brightener, bis-(anilino ~,~ die~hanolamino triazinyl) stilbene disul~onic acid, another .. ~ - . .
~tilbene brightener, sodium bis-(~nilino morpholino triazinyl) stilben~ di~ulfonate; and an oxazole brightener, having a 1-phen~l 2-benzoxazole ethylene structure, 2-styryl naphtho ~, 2 ~ oxazole, in the relative proportions of about 1:1:3:1.2.
Another minor ad~uvant used may be a foam stabilizer " .
such as an alkanolamide. Such alkanolamide is a higher fatty acld lower mono- or dialkanolamide or the condensation product ,,,-.
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,~., .''' ~: thereof with a lower alkylene oxide of the type described above ` when discussing nonionic detergents. The fatty acid or acyl ,:,, ~ portion of the alkanolamide contains from 8 to 16, preferably 10 ,:........................................... .
i to 16 carbon atoms. For example, the acyl portion may be ~:, ' 5~ derived from lauric acid, myristic acid or coconut oil fatty , .
, . . .
~ acids or a mixture of these. The lower alkanol portion of the : , alkanolamide is of 2 to 3 carbon atoms and can be derived from ~` ethanol, isopropanol and n-propanol, in that order of preference `~ with the monoalkanolamides, ethoxylated or not, being preferred.
The alkanolamide-alkylene oxide condensates which are more . .. .
preferably employed as foam stabilizers can contain from 1 to 50 . ~ . . .
alkylene oxide residues per molecule, preferably 1 to 10, more prefarably 1 to 6 and most preferably 4 to 5.
- An oryanic solubilizing agent such as urea or a water `j~$ -~; 15 soluble surface active lower alkyl benzene sulfonate salt may also be incorporated in the paste as a functional adjuvant.
:. i , - , ~-~ Such agents not only aid in solubilizing the other ingredients ~; of the compositi~n but also may desirably modify the viscosity of the paste and often may act as thinning agents. The lower ` 20 alkyl benzene sulfonate salt solubilizing agents contain 1 to 3, preferably 1 to 2 lower alkyl substituents in the benzene nucleus , the lower alkyl substituents being exemplified by s~ methyl, ethyl, n-propyl,isopropyl and isobutyl groups. The ~` cation associated with the lower alkyl benzene sulfonate s.
~ 25 solubilizing agent is similar to those discussed above for use j~ ~ with water soluble anionic detergents and preferably is alkali metal or ammonium with sodium and ammonium,being especial-ly preferred.
. . .
, ..
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,, 1~58i~

When the detergent paste i5 used for washing by hand it is advantageous to include a skin protection or conditioninq - agent as an adjuvant, such as a material which increases the mildness of the detergent composition to human hands. Of such `~ 5 compounds the water soluble proteins are highly preferred. Such materials are low molecular weight polypeptides obtained by hydrolysis of protein materials such as animal hair, hides, gelatin, collagen and the like. A particularly preferred water soluble enzyme is made by hydrolysis of pork protein. During hydrolysis the proteins are gradually~ broken down into their constituent .,~ ~ , .
!''.; polypeptides and acids by prolonged heating with mineral acid or alkali or by treatment with enzymes, e.g., peptidases. During ,.
.
~i hydrolysis products made are converted progressively to simpler ~;~ peptides, e.g., tripeptides, dipeptides, and finally to amino acids. The polypeptides derived from proteins are complex mixtures .. ;.~ .
~; and in practice the average molecular weight of the hydrolysate .~, .
will vary from 120 (amino acids~ to about 20,000. The satisfactory hydrolyzed polypeptides are characterized by water solubility.
,~ ,. ..................................................................... .
~'- In compositions containing soluble protein it is often preferred to employ hydrolyzed collagen of such low molecular weight as to be completely soluble in water, non-gelling (exhibiting zero Bloom value) and non-denaturing, with an average molecular -~ weight below 15 r 000 ~ preferably in the range of about 500 to ",~ . 10, 000.
. 25 Other important functional or aesthetic adjuvants :.i .
;~ for the detergent pastes include enzymes, e.g., proteases, .
~`; amylases; foam destroyers, e.g., silicones; fabric softeners, . .. .
.... . . . .
,. . .
,, - .

.

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~. .
-~ e.g., ethoxylated lanolin; bactericides, e.g., tetrachloro-....
~- salicylanilide, hexachlorophene, trichlorocarbanilide; thicken-ers, e.g., starches, gums, alginates, celluose derivatives;
opacifying agents, e.g., behenic acid, polystyrene suspensions, ~; 5 castor wax; buffering agents~ e.g., alkali metal borates, acetates, i :
bisulfates; and perfumes.
-; The detergent pastes are "fluids" whlch retain their ; activity and homogeneity over a long shelf life, e.g., over a year. Their fluidity makes them feasible to measure or meter.
They can be employed as industrial or household detergents, for i , example for washing dishes, but are prefera'~ly used for washing . ~. . I -i clothes, especially in automatic washing machines. In launder-., "
~. ing clothing in automatic washing machines the amount of deter-.. . . . . .
gent paste which is used in the wash water will, of course, vary i~ 15 somewhat depending on the type of washing equipment used. In ,`"'`~!`~` . general however, only a relatively small concentration of the ~ paste detergent in the wash water,amounting to 0.1 to 0.3~, ,.~
preferably about o.ls~, is used for a full tub of wash (4 to ~ 15 lbs.) employing either a top loadiny (vertical axis agitator "!.~`~'',~'' 20 type) or front loading (horizontal tumbling drum type) washing ... j . ~
~ machine, in which the water volume is from 5 to 20 gallons, ,;~
~ usually from-15 to 18 gallons. A concentration of as little as ; about 0.07 to 0.2~ of the detergent in the wash water may be., ~, .
employed for front loading machines. For "European" washing .. . .
machines, which use less water, the paste concentration may increase to 2 to 3 times that which is normal for top loading machines.
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The paste detergent composition of the invention is highly effective in washing clothes, even in very hard waters .... .
(over lS0 p.p.m. or greater hardness, as CaC13) but preferably -a moderatPly soft water is used with a hardness less than 150 .::. ' .
p.p.m., preferably of 25 to 100 p.p,m. While the washing tempera-ture employed with the present paste detergent can range from ~`~`; I0 to 90C., preferably it is from about 20 to 70C. Thewashing is usually followed by rinsing and spinning or other ,. . .
. draining or wringing cycles or operations, which are preferably ; 10 automatic. Of course, the present paste detergent may also be .: . . .
~ used or manual washing of laundry. In such instances it may be ...
~; used full strength or certain stains or heavy soils or thelaundry may be soaked in wash water containing a higher than .,;~ . .
.
normal concentration of the detergent prior to normal machine washing. The washing operations will generally take from 3 minutes j~ to one hour, depending on the fabrics being washed and the degrees of soiling of the clothing. After completion of the washing and the spinning, draining or wrin~ing operations it is preferred to dry the laundry in an automatic dryer soon thereafter but .
~ 20 line drying may also be used. A fabric softener rinse may be ~ .
interposed between washing and drying or at another suitable , . . . .
stage in the laundering or drying process.
The molecular sieve zeolite~containing detergent pastes : of the invention have been found to be effective detergents to :; . ~. .
~ 25 remove a wide variety o soils, including clay and carbon soils, ..... . . .
skin soils, natural and artificial sebum soils, fatty soils, proteinaceous soils and especially,particulate soils from a :: -~ variety of fabrics, including cotton, nylon, polyester, s~lch . ~ .
as polyethylene terephthalate, Eotton-polyester blends, cotton-nylon blends and nylon-rayon-cotton blerlds.
:
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, .. .

...

~58~
Even when devoid of a conventional builder salt ingredi-ent, the present paste compositions are highly effective detergents due to the excellent detergency building effect of the molecular sieve zeolite ingredient. The molecular sieve zeolite components are highly efficient in sequestering calcium ion and preventing detergent precipitation, as is illustrated by their aforementioned excellent performance in laundering operations carried out with wate~ of high calcium hardness. The silicate builder component helps to counteract any magnesium hardness in the water and ~he :. .
~ 10 silicate is more stable in the paste products than in liquids.
... ~ . .
Surprisingly, the paste form of the detergent composition contain-ing the molecular sieve æeolite is capable of removing calcium ion , .
~ from the wash water in cold water washing faster than is the case .: t for spray dried products of similar formulation.
The zeolite sieve gives desired body to the detergent preventing it from beiny too soEt, and allows the incorporation of larger quantities of various ingradients that would not be stable in liquids and would settle out in them, e.g., silicates. The .. ~ .: . . . .
~ paste form is also often aesthetically preferable.
i:
On washing of fabrics with the present paste detergent only slight, almost unnoticeable deposits of insolubles remain on the fabric after rinsing, even in the absence of an anti-redeposi-tion agent and in the absence of machine drying. It was surprising to discover this excellent anti-redeposition characteristic of the present detergent in view of the known water insolubility of the molecular sieve zeolite component of the detergent pasteand .... .
- the quantity-thereof present. When automatic drying is employed -~ the washed laundry does not even have a noticeable deposit of molecular sieve on it. Also, white fabrics washed with the ` 30- present surfactant mixtures in the presence of colored fabrics - are no~ stained by dyes ~ugitive from the colored fabrics when ordinary washing and drying methods are employed.
,:
.... .
....
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- 21 ~
... .

~ s~40 . .
' Thus, the present paste detergents can be made in stable paste form, without the need for phosphate builder salts ` . - and the molecular sieves used as primary builders to counteract . calcium hardness,also tie up water in the paste and contribute ;~ 5 significantly to making the paste or gel and stabilizing it on ~ .
~ storage.
.
~:: . The following examples illustrate the invention but do . not limit it. Unless otherwise indicated, all parts are by . ~ .. . . .
.~ weight and temperatures are in C.
... . .
~,~ .~ .. .

~ Nonionic detexgent (1) 15 .,~, ,; .
: Sodium silicat0 (2) 15 . Molecular sieve zeolite (3) 25 ,. .. .
Sodium caxboxymethyl cellu:lose 0.5 Deionized water - 44.5 ' '" 100. 0 ., ~ .

(1) Neodol 25-7 C12_15 linear primary alcohol ethoxylata -:. . containing on the average 7 ethylene oxide residues per ,,~ ., .
i~`` molecule (Shell Chemical Co.) ..
.~.;. 20 (2) Na2O:SiO2 - 1:2.35 ~ (3) Sodium aluminosilicate having type A crystalline structure, i;`~',`, .
:'`. a nominal pore size of 4 Angstroms, an average particle ~.',.', ' .
~;. diameter of 6.4 microns, and a moisture content of about.
, ....
`:. 21% (percentages of molecular sieve zeolites given in this and the following examples are on an anhydxous basis) manufactured by Henkel & Cie.
. .~, .
~;~; The components are admixed and then mixed for about 5 i .i."'' ,..':
:, . .
. - 22 ,, .

~5~
minutes at room temperature (25~C.). The resulting mixture is a stable homogenous fluid paste which can be extruded easily.
When tested at a wash water concentration of about O.I.~ in an .i,, automatic washing machine the paste exhibits an excellent detersive effect against clay and carbon soils, skin soil, natural . ~ .
; and artificial sebum soils and especially particulate soils on cotton, nylon, polyester and cotton-polyester blend fabrics.
; The detergent paste is tested for detersive effects toward particulate soils against a commercial liquid detergent, , i . .
conventional laboratory and practical laundry mixed soil tests.
The differences between the soil removal index value for the present paste and that for the commercial liquid deter-' gent indicate a superior detersive effect of the present `; detergent especially against particulate soils.
:,, .
Substantially the same type of excellent results is obtained when the molecular sieve zeolite is replaced in the ;A formula given by a molecular sieve zeolite having a type A
crystalline structure, an average por size of 8 Angstroms, nominal an average particle size of 8.3-microns and a moisture content of ;- 20 21~ (Linde Type 4A molecular sieve, manufactured by Union ~ Carbide Corp. and ~ested in hot (50C.) and cold (20C.) waters.
... .

` EXAMPLE 2 "., %
.:.
- Nonionic detergent 1 .;; 25 (as in Example 1) - Sodium silicate 12 tas in Example 1) ~olecular sieve zeolite 24 ~ (as in Example 1) : ,.,.:.
~ 30 Deionized water 48 ',~. 100 . O
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. .
The above rnaterials are mixed together substantially as described in Example 1. There is obtained a paste having an excellent homogeneity, "fluidity" and detersive effect similar to that of the product of Example 1. When the paste is comparative-ly tested against a liquid detergent(product) according to astandard mixed soil testing procedure, as in Example 1, it -, receives an excellent rating for particulate soil removal, .~, . .
substantially similar to that achieved by the Example 1 product. -~'~ This is also the case when the nonionic detergent is replaced by ,~ 10 Neodol 45-11, Alfonic 1618-65 and Igepal C0-630, at least to ; ~, the extent of S0% replacement. A good, stable product also results when half the silicatce is replaced with sodium carbonate, .....
pentasodium tripolyphos~phate or trisodium nitrilotriacetate or ;"' ~ a mixture thereof in equal parts.
. ~ .
; EXAMPLE 3 %

~` Nonionic detergent 33~1 ~i (as in Example 1) ~` Sodium silicate 11.1 ~` 20 ~as in Example 1) ~ Molecular sieve zeolite 30.6 -~ (as in Example 1) ,. . .
; ~ Sodium carboxymethyl cellulose 0.2 Deionized water 25 ;;i ~. - 1 0 0 . O

~; 25 The procedure of Example 1 is utilized to prepare a homogeneous stable paste of the above formula which exhibits excellent detersive effects against various type of soils in ,i,.,~, . .
~` practical laundry tests in home laundry top and front loading automatic washing machines at 0.2 and 0.1~ concentrations `~ 30 respectively (water hardness of ~0 p.p.m., as CaC03, 60% of which , ,. ' .,, ~.~
. ., , :.
~i - 2~ -~.......................................................................... ;
. . ~

s~

is calcium hardness and 40% of which is magnesium hardness).
. .
Anti-redeposition is improved by the presence of the :` .
CMC and is further bettered by an increase thereof to 0.5%.
. Polyvinyl alcohol, when substituted for the CMC,is also effective as an anti~redeposition agent. Both CMC and PVA help to strengthen the gel or paste made. ~Tap water can be substituted for the .j, I .
`~ deionized waterO Also, other molecular sieve zeolites of A12O3:
' SiO2 molar ratios of 1:1 to 1:4 may be used successfully.
~i~ EXAMPLE 4 . . . .
:.-~, ';'` 10 ., ~Nonionic detergent 43.5 -~; (as in Example 1) Molecular sieve zeolite 44.5 (as in Example 1) . ...... .
15~ Deionized water 12.D
:. .~ .
The procedure of Example 1 is utilized to prepare a useful deterg en~ paste from the above ingredients. The product ~ . . .
~ exhibits an excellent detersive~effect and is e~pecially good .~,, . ~ .
for hand and machine washing and for lighter duty detergent . applications.
;
,. . .
~ ~.......................... .
', EXAMPLE 5 .i %
~;. ., _ ..
Nonionic detergent 24 (as in Example 1) ~' Sodium silicate 8 -~ (as in Example 1) : .
Molecular sieve zeolite 24 ; (as in Example 1) ` Sodium carboxymethyl cellulose 0.2 ` Deionized water 34.7 ,: :: .
~, Anionic detergent (4) 9.1 .: :.
;~'' _ 25 . ., :.:

S~

(4) Linear sodium dodecyl benzene sulfonate.
The above materials are made into a paste in accord-`: ance with -the procedure of Example 1. There is obtained a stable homogeneous paste detergent which is excellent for . . .
laundering soiled clothing in automatic washing machines but , iS al80 ~uitable for hand laundering. The prPsence of the anionic detergent i~proves the cleaning power of the detergent i~ pa~te and the ph~sical ~orm.
, .
` In the above examples the proportions o~ components are chang~d w~thin the ranges prevlou~ly given and good paste deterg~nts are mada. Al~o the var~ou~ molecular sieves (Types X, Y, L, chabazi~e, erionite and mordenite), detergent~3 builder ~alt~ and ad~uvants are substituted and added, within the limit~
given and good, ~table, convenient to use products are the . .
` 15 results. ~uch pastes re~uire little energ~ for their manu~ac-.
ture, are non-p~lluting (when pho~phates are avoided) and are made by a simple non-pollutlng process. They are concentrated ~` and eas~ to use. Best of all, the products are effective cleaners and do not deposit objectiona~ly on the laund~y.
... .. .
~0 As indicated heretofore, the method o~ washing laundry which comprise~ contactlng it with an aqueous medium containing , ` a ~t~ble homogeneous paste detergent compris~ng a ~a~er ~oluble ,,~.;
synthetic organic detergent and a particula~e molecular sieve , i, ~
zeollte builder in cation-exchanging form also forms part of ..~, this invantion~ In a preferred method, the paste detergent ; employed eo~prises 5 to 50% of sodium higher linear alkyl ~"~ benæene sulfonate detergent, 5 to 60% of the molecular sieve .; ,., ~,, ~ - 26 ;..
, -; .
....
j,., '`~';
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~ .

zeolite in univalent cation-exchanging ~rom and 10 to 70%
of water and the paste is initially applied to selected items of the laundry be~ore addition thereo~ to the wash water to help remove stubborn soil and stains theref~om.
. : 5 The invention has been described with respect to ' working examples and illustrations thereo~ but is not to be . .~
. limlted to the~e because it is evident that one of skill in ~, the art with access to the present speci~ication will be , .
able to employ ~ubstitutes and equivalents without departing ~rom the spirlt or scope of the invention, : -`, ' . ~

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Claims (14)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
   PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   
   l. A stable, homogeneous paste detergent composition comprising 5% to 50% by weight of a water-soluble, synthetic organic detergent, 5% to 60%
   by weight of a water-insoluble molecular sieve aluminosilicate zeolite builder effective to sequester calcium ions selected from the group consisting of Type A, X, Y, L, mordenite and erionite, said zeolite being in the form of particles having a mean particle diameter of from 0.5 to 12 microns, having a univalent cation selected from the group consisting of sodium, potassium, lithium, ammonium and hydrogen, and containing 1.5% to 36% by weight of water, and 10% to 70% by weight of an aqueous medium.
2. 2. A paste detergent according to claim l wherein the organic detergent includes a nonionic detergent, the molecular sieve zeolite builder is select-ed from the group consisting of types A, X and Y, there is present 5 to 35%
   of a water soluble builder and the aqueous medium is water.
3. 3. A paste detergent according to claim 2 wherein the nonionic suf-factant is a higher alkyl poly-lower alkoxy alcohol, the water soluble builder is an inorganic builder salt and 8 to 20% is present and the molecular sieve zeolite is a type A zeolite containing an alkali metal cation as the univalent cation thereof, said alkali metal cation being selected from the group consisting of sodium and potassium.
4. 4. A paste detergent according to claim 3 wherein the nonionic detergent is of the formula RO(C2H40)nH
   
   wherein R represents the residue of a saturated alcohol of 12 to 18 carbon atoms and n is an integer from 6 to 20, the inorganic water soluble builder salt is an alkali metal silicate having an alkali metal oxide to silica molar ratio of about 1:1.5 to 1:3.2, the molecular sieve zeolite is a synthetic sodium zeolite in water-loaded form and there is present 0 to 20% of functional or aesthetic adjuvants selected from the group consisting of organic anti-redeposition agents, organic foam stabilizers, organic solubilizers, colorants, organic optical brighteners, opacifying agents, skin protection agents, buffers, fabric softeners, enzymes, bactericides, foam destroyers, thickeners and perfumes.
5. 5. A paste detergent according to claim 4 wherein the molecular sieve zeolite is of a mean particle diameter of about 5 to 9 microns, the alkali metal silicate is sodium silicate having a sodium oxide to silica ratio of about 1:2 to 1:2.5 and there is present as an adjuvant 0.2 to 2% of an organic anti redeposition agent.
6. 6. A paste detergent according to claim 5 wherein the R substituent of the nonionic surfactant is the residue of a linear primary alcohol of 12 to 15 carbon atoms, n is about 7 to 11, 15 to 35% of the nonionic detergent is present, the sodium silicate is of Na20:SiO2 ratio of about 1:2.35, the molecular sieve zeolite has a mean particle diameter of about 6.4 to 8.3 microns and a pore size of about 4 Angstroms and 20 to 35% is present, the aqueous medium is deionized water and 25 to 50% is present and the organic anti-redeposition agent is an alkali metal carboxymethyl cellulose and 0.2 to 0.5% is present.
7. 7. A paste detergent according to claim 1 consisting essentially of about 16% of nonionic detergent, 12% of sodium silicate of Na20:SiO2 ratio of about 1:2.35, 24% of the molecular sieve zeolite and 48% of water.
8. 8. A paste detergent according to claim 6 consisting essentially of about 15% of the nonionic surfactant, 15% of the sodium silicate, 25% of molecular sieve zeolite, 0.5% of sodium carboxymethyl cellulose, and 44.5% of water.
9. 9. A paste detergent according to claim 6 wherein there is also present 2 to 25% of a water soluble synthetic organic anionic detergent.
10. 10. A paste detergent according to claim 9 wherein the anionic detergent is an alkali metal organic sulfonate or sulfate and 5 to 12% there-of is present.
11. 11. A paste detergent according to claim 10 wherein the synthetic organic anionic detergent is a sodium higher linear alkyl benzene sulfonate.
12. 12. A paste detergent according to claim l wherein the synthetic organic detergent is a mixture of nonionic and anionic detergents.
13. 13. A paste detergent according to claim 4 wherein the synthetic organic detergent is a mixture of the nonionic detergent and a higher alkyl benzene sulfonate salt.
14. 14. A method of washing laundry which comprises contacting it with an aqueous solution having a temperature from 10°C to 90°C and containing from .07 to 0.9% by weight of a stable homogeneous paste detergent composition comprising 5% to 50% by weight of a water-soluble, synthetic organic detergent 5% to 60% by weight of a water-insoluble molecular sieve aluminosilicate zeo-lite builder selected from the group consisting of Type A, X, Y, L, mordenite and erionite, said zeolite being in the form of crystalline particles having a mean particle diameter of from 0.5 to 12 microns, having a cation selected from the group consisting of sodium potassium, lithium, ammonium and hydrogen, beingeffective to sequester calcium ions and being in a hydrated form wherein 1.5% to 36% by weight of water is present, and 10% to 70% by weight of an aqueous medium.