CA1052658A - Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method of treating soiled textiles, wherein the soiled textiles are immersed in an aqueous liquor which con-tains at least two compounds inhibiting alkaline earth metal ion precipitation on said soiled textiles comprising using (1) from 0.2 to 10 gm of anhydrous active substance per liter of at least one finely-dispersed, water-insoluble silicate compound having a calcium-binding power of at least 50 mg CaO/gm of anhydrous active substance and having the formula, combined water not shown (M2/nO)x . Me2O3 . (SiO2)y where M is a cation of the valence n, exchangeable with calcium, x is a number of from 0.7 to 1.5, Me is aluminum or boron, and y is a number from 0.8 to 6, and (2) from 0.05 to 2gm/1 of at least one of certain complex polycarboxylates and/or poly-phosphonates, as well as washing compositions containing said at least two compounds.

- A -

Description

~05, ~;5B

As known, the detergents used in the household, in co~nercial establishments and in industry, frequently contain large quantities of condensed phosphates, particularly tripoly-phosphates. These are provided to sequester the hardness formers of tap water and are responsi~le to a great extent for increasing the cleaning power of the capillary-active washing substances. The phosphorus content of these agents has been critici~ed by the public in connection with questions of the protection of the environment. The view is frequently ex-pressed that the phosphatesJ which arrive in the rivers andlakes after treatment of the sewage, have great influence on the eutrophication of the waters, and i8 said to lead to an increase of the growth of algae and of oxygen consumption. It has therefore been tried to eliminate phosphate from the wash-ing and cleaning processes or fro~ the agents used for this purpose, or at least to substantially reduce its proportion.
Copending, commonly-assigned Canadian Patent Application Serial No. 197,628, filed April 16, 1974 disclose~ a process ~or the washing, bleaching or cleaning of solid materials, particularly textiles, by treating these materials with a liquor containing compounds able to bind the ` cationæ that make water hard. The process is characterized in that finely-di~persed, water-insoluble silicate compounds having calcium-binding capacity of at least 50 mg CaO/g~ of anhydrous active substance (AS) and having the formula I, combined water not shown (M2/nO)X Me203 (Si2)y (I) where M is a cation of the valence n, exchangeable with calciu~, x is a number from 0.7 to 1.5, Me is aluminum or boron, and y is a number from 0.~ to 6, preferably from 1.3 to 4, are suspended in the aqueous treatment bath The 1135'~f~5B
process of the patent makes possible the complete or partial replacement of phosphates that bind calcium ions by complexing and are still being used in the ~ashing and cleaning process.
The calcium-binding capacity of the above-defined com-pounds may reach val~es of 200 mg CaO/gm AS and is preferably in the range of 100 to 200 mg CaO/gm AS. The above-defined compounds capable of binding calcium are referred to as "aluminosilicates" in the following text, for the sake of ~im-plicity. m is applies particularly to the sodium alumino-silicates that are to be used preferably. All data given fortheir preparation and processing apply accordingly to the to-tality of the above aluminosllicate compounds as defined in said earlier application.
The cation M employed is preferably sodium. However, the same can also be totally or partially replaced by other cations exchangeable with calcium, such as hydrogen, lithiwm, pota~sium, ammonium or magnesium, as well as by the cations of water-soluble organic bases, for example, by those of primary, secondary or tertiary alkylamines or alkylolamines with not 20 more than 2 carbon atoms per alkyl radical, or not more than 3 carbon atoms per alkylol radical.
This process is indicated as being further i~proved in ~ that the removal of soil is considerably improved when another .J compound is employed in the liquor which has a sequestering and/or precipitating e~fect on the calcium which is contained in the water as a hardening substance. Disclosed as suitable as sequestering agents for calcium were also substances with such a low sequestering power that they were not considered heretofore ~ as sequestering agents for calcium. However, these compounds 30 frequently have the capacity of delaying the precipitation of calcium carbonate from aqueous solutions.

-2-..

105'~S8 ~

Preferably, amounts of sequestering or precipitating ag~ents of, for example, 0.05 to 2 gm~lJ were added to acceler-at~s or i~prove the removal of dirt. Preferred are amounts of 0.1 to 1 g.n/l. Substant~ally larger amounts can also be used, but if phosphorus-containing sequestering or precipitating agents were used, their amount had to be so selected that the phosphorus load of the sewage was much less than with the presently used triphosphate-based detergents.
Copending, commonly-assigned ~anadian patent applica-tion Serial No. 198,560, filed April 30, 1974 discloses an improvement in the above invention, consisting of the presence, in the aqueous liquor together with said aluminosilicates of from 1 part by weight of nonionic surface-active compounds and from 0 to 3 parts by weight of anlonic surface-active compounds, as said surface-active compound, said nonionic surface-active compounds being a mixture of a compound having a labile hydrogen and from 8 to 18 carbon atoms ethoxylated with from 8 to 20 ethylene oxide units and a compound having a labile hydro-gen and from 8 to 18 carbon atoms ethoxylated with from 2 to 6 ethylene oxide units in a weight ratio of 1:0.2 to 2. An im-proved soil removal, particularly in the case of fatty and oily soils, is achieved by the combination of the alu~inosilicates with the above-described tenside component.
; An ob~ect of the present invention is the development of a process of treating soiled textiles by contacting soilêd textiles with an aqueous liquor containing at least two com-pounds inhibiting alkaline earth metal ion precipitation on said soiled textileæ as well as optionally at least one surface-active compound for a time sufficient to disperse or dissolve the soil from said soiled textiles into said aqueous liquor, separating said aqueous liquor and recovering said textiles substantially soil-free, comprising using (1) from 0.2 to 10 g~

-3-,~

lOS'~:t;58 of anhydrous active substance per liter of at leaæt one finely-dis,persed, water-insoluble silicate compound containing at least some combined water and having a calcium binding power of at least 50 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2/n)x Me23 (~i2)y where M is a cation of the valence n, exchangeable with calcium, x is a number of from 0,7 to 1.5, Me ~s a member selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, and (2) from 0.05 to 2 gm per liter of at le~st one water-soluble compound selected from the group consisting of the free acid and acld salts of cations exchangeable with calcium of the following acids:
A) An azacycloalkane-2,2-diphosphonic acld having the formula (CH2)m/ P03H2 C
/
R3 ~ N P3H2 ` wherein m is an integer from 3 to 5 and R3 is æelected from the group consisting of hydrogen and alkyl havlng 1 to 3 carbon atoms, . 20 B) A cyclic aminophosphonic acid having the formula Rl - N . P - OH

O ~ G C ,--\ /\
~ CH2 )p P3H2 wherein p is an integer from 1 to 3 and Rl is selected from the : group consisting of hydrogen and alkyl having 1 to 6 carbon atoms,

-4-~05,~658 C) Pyrrolidone-5,5-diphosphonic acid and N-alkyl-pyrrolidone-5,5-diphosphonic acid where alkyl has from 1 to 6 carbon atoms, D) A copolymerizate of an ester of an alkenol having from 3 to 6 carbon at~ms with a lower alkanoic acid with a maleic compound selected from the group consisting of maleic acid and ~aleic acid anhydride in substantlally a 1:1 ratio, where any anhydride groups are predominantly hydrolyzedto a~id groups, E) Poly- a -hydroxyacrylic acid with a molecular weight of at least 20,000, ; F) A copolymeri~ate of a vlnyl-lower alkyl ether with a maleic compound selected from the group consisting of ~aleic acid and maleic acid anhydride in substantially a 1:1 ratlo, : where any anhydride eroups are predomlnantly hydroly~ed to acid groups, G) 3-a~ino-1-hydroxypropane-1,1-i~iphosphonic acid, H) A polyphosphonlc acld having the formula ,~ ' Y~ 1 03H2 ~ ~C X

wherein X is a member selected from the group consisting of H, ::' OH, NH2 and Cl and Y is a member selected from the group con-.i:
sisting o~ hydrogen and halogen, with the proviso that when X is NH2, Y is halogen, and . I) A citric acid pyrolyzate having at least 4 carbo~yl groups per molecule and at least one olefinic-unsaturation, and the bisulfite addition product thereof.

-5-~(~5'~SI~

A further ob~ect of the present invention is the develop-ment of a detergent system for washing soiled textiles comprising the above water-insoluble silicate compound, the above water-soluble compounds, and a low to zero phosphate textile detergent.
These and other ob~ects of the invention will become more apparent as the description thereof proceeds.
As described in Serial No. 197,628, soil removal is improved considerably when a substance is added to the liquor that has a complexing and/or precipitating effect on the calcium ions present as a hardening constituent in the water. It has now been found that a series of such compounds are especially suitable for use in the process.
Thus, the present invention relates to an improved pro-cess for the washing and bleaching of textiles by treatment of the same with an aqueous liquor containing substances able to sequester the compounds that make the water hard, where finely-dispersed, water-insoluble silicate compounds containing at least some combined water and having a calciu~ binding power of at least 50 mg CaO/gm of anhydrous active substance and the /1, fornula (I) on the anhydrous basis (M2/nO)X . Me203 (sio2)y (I) where M is a cation ofthe valence n, exchangeable with calcium, x is a nw~ber from 0.7 to 1.5, Me is aluminum or boron, and y is a number from 0.8 to 6, preferably from 1.3 to 4, suspended therein, as well a~ an organic calcium-complexing or precipi-tating builder, and where the aqueous liquor also optionally contains a surface-active compound, characteri~ed in that one of the following compounds, capable of binding calcium, is present as a builder in the for~ of free acid or as a water-soluble salt ~ 30 thereof:

`~ _6-1(~5'~;51~
A. An azacycloalkane-2,2-diphosphonic acid of the fo~ula ( CH2 )m P3H2 \C/
1 / \
R3 _ N P3H2 where ~ stands for 3 to 5 and R for a hydrvgen or an alkyl with 1 to 3 carbon atoms;
B.. A cyclic aminophosphonlc acid of the general formuhII-Rl - T p _ OH

O = C C NHRl (II) (C~2)p P03H

where R stands for an alkyl with 1 to 6 carbon atoms or a hydro gen atom and p for a number from 1 to 3; `~ ;
C. Pyrrolidon-5,5-diphosphonic acid in which the hydro- `
gen on the nitrogen may be replaced by an alkyl with 1 to 6 carbon atoms;
. . ~
~ D. A copolymerizate o~ a mono-unsaturated mono-alcohol - esteri~led with a carboxylic acid, with maleic acid or ~aleic acid anhydride in a 1:1 ratio, where the anhydride units are mainly hydrolized under the conditions of application;
E. Poly-a-hydroxyacrylic acid with a ~olecular weight of ~1 at least 20,000;
.~, F. A copolymerizate of a polyvinylalkyl ether and maleic acid or maleic acid anhydride, where the alkyl contains :~1 1 to 6 carbon atoms and the a~hydride units are ~ainly hydrolized under the conditions of application;
G. 3-Amino-l-hydroxypropane-l,l-diphosphonic acid;

; -7-1(~5'~658 H. A polyphosphonic acid of the general formula III

y P3H2 ~ X (III) where x stands for H, OH, NH2 or Cl and Y for H or halogen, where, when X ls NH2, Y is halogen; and I. A citric acid pyrolyzate.
All compounds of A to I are water-soluble and/or capable of forning water-soluble salts.
More particularly, the present invention iB directed to :`. a process of treating soiled textiles by contacting soiled textiles with an aqueous liquor containing at least two com-. pounds inhibiting ~lkaline earth metal ~on precipltation on sald soiled textiles as well as optionally at least one surface-: actlve compound for a time sufficient to disperse or dlssolve the soil from said soiled textlles into said aqueous liquor, separating said aqueous liquor and recovering said textiles ~ æubstantially soil-free, comprising using (1) from 0.2 to 10 gm i` of anhydrous active substance per liter of at least one finely-dispersed, water-insoluble silicate compound containing at least æone combined water and having a calcium binding power of ~-~ 20 at least 50 mg CaO/gm of anhydrous active substance and the . formula on the anhydrous basis , 1~ . (M2/n )X ~ Me23 ~ (si2 )y . where M is a cation of the valence n, exchangeable with calciun, x is a nwmber of fron 0.7 to 1.5, Me is a menber selected from the group consisting of aluminun and boron, and y is a number ~ from 0.8 to 6, and (2) from 0.05 to 2 gm per liter of at least .~ one water-soluble compound selected fron the group consiæting of the free acid and acid salts of cations exchangeable with 1(~5'~658 ca:Lcium of the following acids:
A) An azacycloalkane-2,2-diphosphonic acid having : the formula (CH2)01 ~ P03H2 `:
\ C ~`
/ \
R3~N ~ P03H2 wherein m is an lnteger from 3 to 5 and R3 i8 selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon : -. .
atoms, .~
B) A cycllc aminophosphonic acid having the formula ~ --O ..
Rl - N P OH -;

NHRl , O = C C~ .~ -'f (CH2)p P03H2 wherein p i8 an integer from 1 to 3 and Rl is selected from the group consisting of hydrogen and alkyl having 1 to 6 carbon atoms.
C) Pyrrolidone-5,5-diphosphonic acid and N-alkyl-pyrrolidone-5,5-diphosphonic acid where alkyl has from 1 to 6 carbon atoms, ;: D) A copolymeri~ate of an ester of an alkenol having from 3 to 6 carbon atoms with a lower alkanoic acid with a maleic compound selected from the group consisting of maleic i acid and maleic acid anhydride in substantially a 1:1 ratio, 1 20 where any anhydride~-groups are predomLnantly hydrolyzed toacid groups, E) Poly-a-hydro~yacrylic acid with a molecular weight . of at least 20,000, F) A copolymerizate of a vinyl-lower alkyl ether with a g_ ., 1(35'~65~

maleic compound selected from the group con~sting of maleic acld and maleic acid anhydride in substantially a 1:1 ratio, where any anhydride groups are predo~inantly hydrolysed to acid gr'OUp8, G) 3-amino-1-hydroxypropane-1,1-ldiphosphonic acid, H) A polyphosphonic acid having the formula y P03H2 ~ C_X
P~3H2 wherein X is a ~ember selected from the group consisting of H, OH, NH2 and Cl and Y is a member selected from the group con-sisting of hydrogen and halogen, with the proviso that when X isNH2, Y ls halogen, and ; I) A citric acid pyrolyzate having at least 4 carboxyl groups per molecule and at least one olefinic-unsaturation, and the bisulfite addition product thereof~ as well as co~positions for general uæe in washing, r,insing and bleaching agent composi- -tions consisting essentially of (a) from 5~ to 95~ by weight of at least one o~ the above water-soluble builders capable of binding or sequestering calclum, and (b) from 95~ to 5% by weight of at least one of the abeve water-insoluble silicate compound~.
The azacycloalkane-2,2-diphoæphonic acids of the above for~ula are described in the copending, commonly-assigned Canadian patent application Serial No.207,802, filed August 26, 1974 These compounds can be prepared by reacting lactams cor-responding to the given formula, but containing a carbonyl group instead Q~ the diphosp~onomethy~ene group, wi~h phosphorus tri-halides or phosphorous acid and phosphorus trihalides, ~: , 1 [)5'~58 hydlrolyzing the reaction product and optionally converting -into a water-soluble salt. Examples for this group o~ compounds are:
azacycloheptane-2,2-diphosphonic acid, azacyclopentane-2,2-diphosphonic acid, N-methylazacyclopentane-2,2-diphosphonic acid and azacyclohexane-2,2-diphosphonic acid.
The cyclic aminophosphonic acids of the general ~ornula II are described in the copending, commonly-assigned Canadian patent application Serial No. 207,800, ~iled August 26, 1974.
These compounds can be prepared according to the process described therein, where dicarboxylic acid derivatives of the formula X - (CH)p-~, where p is from 1 to 4 and X is CN, C~ONH2 or COONHR (R = alkyl with 1 to 4 carbon atoms), are reacted with phosphorus trihalideæ or with phosphorous acid and phosphorus ~ trihalides, the reaction product is hydrol~zed in an acid ; medium, and converted into a water-soluble salt, if desired.
i The reaction of the dicarboxylic acid derivatives with the phos-phorus compounds is performed usually at a ratio of 1:2 to 1:6, preierably at approximately 1:4, Individual examples of this class of compounds are 2-hydroxy-2,7-dioxo-3-amlno-3-phosphonyl-- 20 1,2-azaphosphacycloheptane; 2-hydroxy-2-oxo-3-amino-3-phosphonyl-5-oxo-1,2-azaphosphacycloheptane ; 2-hydroxy-~-oxo-3-amino-3-phosphonyl-6-oxo-1,2-azaphosphacyclohexane; 1-methyl-2-hydroxy-'~J 2-oxo-3-methylamino-3-phosphonyl-6-oxo-1,2-azaphosphocyclo-hexane; l-ethyl-2-hydroxy-2-oxo-3-ethylamino-3-phosphonyl-6-oxo-1,2-azaphosphacyclohexane; l-butyl-2-hydroxy-2-oxo-3-butylamino-3-phosphonyl-6-oxo-1,2-azaphosphacyclohexane and 1-.
methyl-2-hydroxy-2-oxo-3-methylamino-3-phosphonyl-~-oxo-1,2-azaphosphacycloheptane.
The pyrrolidone-5,5-diphosphonic acid as well as its derivatives having a lower alkgl substituted on the nitrogen are described in the cop~nding, commonly-assigned Canadian 1~5 ~ ~ 5 ~

pat;ent application Serial No. 207,803, filed August 26,1~74.
These compounds can be prepared, for example~ by reacting suc:cinic acid derivatives such as succinic acid diamide, which ha~, if desired, a lower alkyl with 1 to 7 carbon atoms on each amide group, with phosphorus trihalides or phosphorouæ acid and phosphorus trihalldes, and subsequent alkaline hydrolysis of the reaction product. Particularly suitable in addition to succinic acid dlamide are the dimethylamide, di-ethylamide, di-propyl-amide and di-butylamide derivatives.
The copolymerizate of an esteri~ied unsaturated mono-alcohol with maleic acid or maleic acid anhydride is derived preferably from a mono-unsaturated primary alcohol or alkenol with 3 to 4 carbon atoms, particularly allyl alcohol esteri~ied with a straight-chain or branched-chain alk~noic acid with 1 to

6 carbon atoms in the molecule. The alk~noic acid is preferably acetic acid or propionic acid. A preferred product, the copoly-merizate of allyl acetate and maleic acid anhydride at a ratio of 1:1, is co~mercially available. The product is available in a molecular weight range of 4,000 to 10,000, however, products with higher molecular weights are also suitable.
Poly-a-hydroxyacrylic acid is o~ered by Solvay & Cie., Brussels. Its preparation is described in German published application DOS 2 161 727, for example. The molecular weight of the polywa-hydroxyacrylic acid is generally above 20,000 and ; particularly above 26,000~ Particularly suitable ha~e been products with molecular weights in the range of 100,000 to ; 140,000. Compounds with higher molecular weights up to the limit of water-solubility are also suitable.
Suitable vlnyl-lower alkyl ether/maleic acid anhydride ~ 30 (or maleic acid) copolymerizates are copolymerizates possessing - an alkyl group with 1 to 7 carbon atoms. The monomer ratio is 1~15'~65~3 preferably 1:1. The molecular weight is at least 1,500, but is usually higher and can be between 100,000 and 2,500,000, for example. A preferred commercial product i8 Gantrez AN - 119 ; with an average molecular weight of 250,000, marketed by GAF
Corporation, New York.
Important representatives of the compounds of formula III are given in the examples.
; "Citric acid pyrolyzate" is understood to mean a commer-cial product of Citrex S.A., Belgium (La Citrique Belge), commer-cially available under the name Citrex~. This is a product that is obtained by the pyrolysis of an alkaline earth metal citric acid salt, at temperatures between approximately 250C
and 400C until the titratable alkalinity rises, and subsequent hydrolysis of the salt to give the unsaturated acid. The product is presumably a mixture of compounds and has an average of 4 or more carboxyl groups per molecule. Especially suitable and in-cluded in the term "citric acid pyrolyzate" is a product that can be obtained by the addition reaction of a bisulfite with the 'i unsaturated acid prepared as described above.
All builder compounds used according to the present in-vention are solids in the anhydrous form. However, in practice ~hey are employed either with a certain moisture content or in aqueous solution. m e given amounts refer to the anhydrous compounds.
;' The compounas A to I are generally employed in ionized ....
-; form in aqueouæ solution. They are used mainly in the form of . .
their water-soluble salts. The cation ions employed are water-soluble cations exchangeable with calcium, preferably the cations of the alkali metals, particularly of sodium and potas-sium, but also of am~oniwm and/or organic ammonium derivatives.
~; m e water-soluble organic base cations which are suitable are, ..... . ..

~S'~658 for exa~ple, those derived from primary, secondary or tertiary alkylamines or alkylolamines with not more than 2 carbon atoms per alkyl or not more than 3 carb~n atoms per alkylol.
The use of the compounds enumerated above as complex-fo~ning substances in the processes or in the compositions of the invention i~ of particular i~portance for products contain-ing little or no phosphates. Exceptionally good phosphate-free detergents and cleaning substances can be prepared according to the invention. As far as these still include phosphate-contain-ing co~pounds, their phosphate content is considerably reduced in comparison to the previously used phosphate-containing deter-gents. The invention thus offers a contribution to the solution of the so~called phosphate problem caused by the overabundance of phosphate, partlcularly in standing bodies of water.
The substances according to the invention contain prefer-ably at least one surface-active compound or tenside. The compo-sition of typical textlle detergents, usable at temperatures of from 50 to 100C, is within the range of the following recipe:
5~ to 40%, particularly 5% to 30% by weight of anionic and/or nonionic and/or amphoteric surface-active compounds, 5% to 70% by weight of the above aluminosilicates, 2% to 45% by weight of the calcium-binding compounds used according to the invention, O to 50~ by weight of wash alkalis that cannot form complexes (alkaline builders), 0 to 50~ by weight of bleaching agents, as well as other ad~uvants, present in most textile detsrg~nts in smaller quantities, The above-defined alu~inosilicates can be produced syn-thetically in a sinple manner, for example, by reacting water--1~)5'~fà58 soluble silicates with water-soluble aluminates in the presence of water To this end aqueous solutions of the starting materi-als can be mixed with each otherJ or one component which is present in solid form can be reacted with another component which is present as an aqueous solution The desired alumino-silicates can also be obtained by mixing both solid components in the presence of water, preferably with comminution of the ; mixture Aluminosilicates can also be produced from Al(OH)3, A1203 or SiO2 by reaction with alkali metal silicate or alkali metal aluminate solutions. Finally, such substances are also formed from the melt, but this method seems of less economical interest because of the required high melting temperature and the necessity of trans~orming the melt into finely-dispersed products, The cation-exchanging aluminosilicates to be used accord-ing to the invention are ohly formed if æpecial precipitation conditions are maintained, otherwise products are formed which have no, or an inadequate, calcium exchanging power. The calcium j exchanging power of at least 50 mg CaO/gm of anhydrous active substance (AS~ is critical to the present process I~ alwmino-silicates are employed with below the critical limit of calcium exchan~ing power, very little if any soil removal from the soiled textiles i8 ef~ected.
, The aluminosilicates in aqueous suspension produced by precipitation or by transformation in finely-dispersed form according to other methods are obtained in an X-ray amorphous ~orm. They can be transformed fro~ the amorphous into the aged or crystalline state by heating the suspension in water to temperatures of 50 to 200C However, there is hardly any dif-ference ~etween these two forms as far as the calcium binding power is concerned. Aside from the drying conditions, the cal-; cium binding power of the alwminosilicateæ is proportional to ~(~5'~:~;5~3 the! amount of aluminum contained therein with reference to the amc)unt of silicon. Nevertheless, the crystalline aluminum sili-cat;es are preferred for the purpose of the invention. The preferred calcium bindlng power~ which is in the range of 100 to 200 mg CaO/gm AS, is found primarily ln compounds of the composi-tion:
0.7 to 1.1 Na20 . A1203 . 1.3 to 3.3 SiO2 This su~mation formula comprises two types of different crystal structures (or their non-crystalline initial products~
which also differ by their summation formulas. These are:
a) 0.7 to 1.1 Na20 . A1203 . 1.3 to 2.4 SiO2 b) 0.7 to 1.1 Na20 . A1203 .>2.4 to 3.3 SiO2 The different crystal structures can be seen in the X-ray dlffraction diagram. The d-values found are given in the e~amples in the descrlption of the production of the alumino-silicates I and II.
The amorphou~ or crystalline alwminosilicate contained in the aqueous ~u~pension can be separated by filtration from the remainlng aqueou~ solution and be dried at te~peratures of 50 to 400C, for example. Depending on the drying conditions, the product contains more or less combined water. Anhydrous products are obtained by drying at 800~C. If it is desired to remove the water completely, thi~ can be done by heating for 1 hour to 800C. This is the way the AS contents of the alumino-silicates are also determined.
Such high drying temperatures are not recommended ~or the aluminosilicates to be used according to the invention, preferably the temperature ~hould not exceed 400C. It is of particular advantage that even products dried at substantially lower temperatures of 80 to 200C, for example, until the ad-hering liquid water is removed, can be used for the purposes of the invention. The aluminosilicates thus produced, which -16_ ~ (~s;~s~
conta~n varying amounts of comb~ned water, are obtained after the disintegration of the dried filter cake, as fine powders whose pri~ary particle size does not exceed 0.1 mm, but i8 mostly lower and ranges down to dust fineness, for example, to 0.1_1. It must be kept ln mind that the primary particles can be agglomerated to larger structures. In some production methods pr~mary partic~e sizes ranging from 30 to 1 ~ are obtained.
Of particular advantage are aluminosilicates having at least 80~ by weight of particles of 10 to 0.01 ~u, preferably 8 to 0.1JU. These aluminosilicates preferably contain no primary or secondary particles above 30 ~. As far as the products are crystalline, they are "micro-crystalline'';
The formation of ~maller particle sizes can already be enhanced by the precipitation conditions. For these smaller particle sizes, the intermixed aluminate and silicate solutions, which can also be introduced simultaneously into the reaction vessel, are subJected to great shearing forces. If crystalline aluminum silicates are produced, which are preferred according to the invention, the formation of larger or inter-penetrating crystals is prevented by slowly stirring the crystallizing mass.
Nevertheless, undesired agglomeration of crystal parti~
cles can occur during the drying, so that it is advisable to remove these secondary particles in a suitable manner, for exa~-ple, by air sifting. Aluminosilicates obtained in coarser form, which are-ground to the desired particle size, can also be used.
Suitable for this purpose are, for example, mills and/or air sifters or combinations thereof. The latter are described, for example, in Ullmann, "Enzyklopadie der technischen Chemie" Vol. 1, 1951, p. 632 to 634.
A considerable improvement in the products, i.e. the washing result with the compounds used according to the lOS~S8 1`
lnvention is achieved by the use of aluminosilicates with lower ca.Lcium-binding capacity.
It is ~lso advantageous for the purposes according to the invention to utilize products that are still moist immedi-ately after their precipitation or even in suspension (without intermediate drying), such as a) a still flowing suspension of aluminosilicate in the liquor in which it is present at the end of the process of preparation, b) an alwminosilicate from which the mother liquor was partially removed, c) a still flowing suspension of aluminosilicate in water, obtained after partial or complete rinsing out of the mother liquor, or d) an aluminosillcate from which the rlnse water was partially removed, What has been said about the primary particles applies , .
to aluminosillcates that are still moist, in suspension or in the form of a ælurry.
From the sodium aluminosilicates, aluminosilicates of other cations, ~or example, those of potassium, magnesium or water-soluble organic bases can be produced in a simple manner by the e~change of bases. The use of these compounds instead of the sodium aluminosllicates may be of advantage if a special effect is to be achieved by the supply of the said cations, for example, if the state of dissolution of different surface-active compounds .
; simultaneoulsly present in the composition is to be in~luenced.
These prepared alu~inosilicates, that is, produced prior to their use, are used for the purposes of invention.
The amount of aluminosilicate required to achieve a good washing effect depends, on the one hand, on its calcium binding :

-105~6S8 power, and on the other hand, on the amount and the type of soil of the textiles to be treated, and on the amount and hardness of the water used. If hard water is used, it is advisable to select the amount of aluminosilicate 80 that the residual hardness of the water does not exceed 5dH (corresponding to 50 mg CaO/l), preferably 0.5 to 2dH (corresponding to 5 to 20 mg CaO/1). In order to obtain an optimum washing effect, it is advisable, par-ticularly for greatly soiled textiles, to use a certain excess of aluminosilicate, in order to bind completely or partially the 10 hardening constituents contained in the released soil, The con-centration of the aluminosilicates can thus be in the range from 0.2 to 10 gm AS/l, preferably 1 to 6 gm AS/l.
Preferably, smaller amounts of the sequestering agents of the invention, for example, 0.05 to 2 gm/l, are employed to no-ticeably accelerate or improve the removal of dirt, Preferred are ~mounts of 0,1 to 1 gm/l Sub~tantially larger amounts can al~o be used, but if phosphorus-containing sequestering or pre-cipitating agentæ are used, their amount should be so selected that the phosphorus load of the sewage is much less than with the presently used triphosphate-based detergents. The amount of the aluminosilicates employed in the wash liquor can be reduced cor-respondingly with the use of larger amounts of the compounds according to the invention.
The use of the above-described aluminosilicates together with the sequestering compounds according to the invention makes it possible to keep the phosphorus content of the wash liquor to not more than o.6 gm/l, preferably to not more than 0.3 g~/l, of organically and/or inorganically bound phosphorus, even with the use of compounds containing phosphorus. However, good results 3 can be obtained without the use of any compounds containing ~; phosphorus, ' , ., .

-105'~58 The process according to the invention op~rating with the use of synthetic, preferably crystailine aluminosilicates, is sultable for the washing, rinsing and bleaching of textiles of all types in the industry in commercial washing establish-ments and in the household.
The textiles to be washed can consist of various fibers of natural or synthetic origin. These include cotton, regener-ated cellulose or linen, as well as text~les which contain high-ly processed cotton or synthetic chemical fibers, like polyamide~
polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers. The detergents according to the lnvention can also be used for washing synthetic fiber- ~ -cotton blends called~1'wash and wear", occasionally also "no-iro~' fabrics When washing by using cleaning liquors containing -alumlnosilicates in aqueous suspension, the washing or cleaning can be improved by common ingredients of these wash liquors.
These include, for example, surface-active compounds, surface-active or non-surface-active foam stabili~ers or inhibitors, textile softeners, neutral or alkaline-reacting builder salts, chenical bleaches, as well as stabilizers and/or activators for - the latter, soil suspension agents, corrosion-inhibitors, anti-microbial substances, enzymes, brighteners, dyes and perfumes.
When using one or several of the above-mentioned sub-- stances, normally contained in wash liquors, the following con-~ centrations are preferably maintained:
-~ O to 2.5 gm/l of sur~ace-active co~paunds O to 0.4 gm/l of activated oxygen or equivalent amounts of activated chlorine as a bleach The terms 'lactivated oxygen" and"activated chlorine"
are employed as meaning bleaching compounds with an _20-.
. . .

1115;~658 oxygen-oxygen bond or a chlorine content, with the given amounts referring to the active oxygen or chlorine, respectively.
The pH-value of the liquoræ can be between 6 and 13, preferably between 8.5 and 12, depending on the type of textile to be washed.
For a long time, attempts-have been made to find a suit-able substitute for phosphates which can not only bind calcium but which are alæo biodegradable in sewage. Various organic compoundæ have, therefore, been suggested as phosphate substi~
tutes. The technical teaching of the invention of using for this purpose water-insoluble cation-exchanging aluminosillcates to-gether w1th the complexing agents of the invention is therefore a complete abandonment of the general directlon in which the in-` duætry has worked. It is particularly surprising that the water-insoluble aluminosil~cates used in the invention are completely washed out from the fabricæ. The use of the aluminosilicates means a rellef of the sewage in two respects. The amounts of phosphorus arriving in the sewage are greatly reduced or com-pletely eliminated, and the aluminosilicates require less oxygen - 20 for biological degradation. They are of a mineral nature, settle gradually in the clarifying plants or in natural waters and thus meet the ideal requisiteæ of a phoæphate æubætitute, But they are also æuperior to other suggested phosphate substitutes in their waæhing action. In particular, they absorb colored soil, and thus save on chemical bleaches.
Baths to be used for textiles according to the invention are prepared by the addition of the substances according to the invention to water. Data for the proportionate amountæ and the nature of the compounds present in the baths also apply to the substances according to the invention, therefore The amount of substance& of phosphonic acid type, present in the materials according to the invention, is preferably not ~, , , ., . .

l(~S'~58 greater than that which corresponds to a total phosphorus con-tent of 6~ in the ~aterial, preferably 3~. These a~ounts are percents by weight. Basically, they refer to anhydrous sub-stances, unless otherwise noted, The calcium complexing, binding and/or precipitating compounds used according to the invention are present in the materials according to the invention preferably in amounts of -~
2~ to 15~. However, they can be used in smaller amounts o~ as low as l~, or in larger amounts of as much as 15~ to 30~
The broad range in detergent compositions i~ therefore from l~ to 45~ by weight. The weight ratio of the substances - used according to the invention to the aluminosilicates of Formula I is frequently approx. 1:8 to 2:1.
The aluminosilicate content of such detergent materials can be in the range of from 2~ to 95~ by weight, generally between 5~ and 95~ by weight, with relatively low alumino-silicate contents o~ from 5~ to 15~ by welght or relatlvely high contents of from 15~ to 60% by weight being preferable, depending , on the type and amount of the compounds used according to the fl 20 invention.
The preferable surface-active compounds or tensldes are the tenside combinations in which compounds with low and high ethoxylation are used optionally, in combination with anionic tensides. The nonionic tensides (nonionics), to be used accord-ingly, are addition products of 2 to 6 or 8 to 18 mols of ~ ethylene oxide to l mol of a fatty alcohol, alkylphenol, fatty s acid, fatty amine, fatty acid amine or alkanesulfonamide, where the fatty moiety is a higher fatty moiety having from 8 to 20 carbon ~toms and alkyl has from 6 to 18 carbon atoms. Particu-larly important are the purely aliphatic nonionics, derived from coconut or tallow fatty alcohols, oleyl alcohol or secondary . . .
, ~ . . . . .
; .. ~

105;~58 alkanols wi~h 8 to 18, preferably 12 to 18 carbon atoms.
Also useable as nonionics are the addition products of ethylene oxide and terminal or non-ter~inal vicinal alkanediols having from 8 to 20 carbon atoms, preferably those with 2 to 4 and 8 to 12 ethylene glycol units, respectively, in the ~olecule.
Also present in the detergents according to the inven-tion may be organic sulfonic acids, carboxylic acids and sulfo-carboxyllc acids that are not surface-active and contain 1 to carbon atoms, These are, for example, water-soluble salts of benzene sulfonic acid, toluene sulfonic acid or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or of sulfodicarboxylic acids.
Wash alkalis are also utilized in the process according to the inventlon or in the detergents according to the invention.
Usually, these amount approximately to 2~ to 35% by weight of the total, Particularly the alkali metal, preferably sodlum, carbonates, dicarbonates, borates and silicates are included under the ter~ "wash alkalis", Particularly important wash alkalis are sodium carbonate and sodium silicate, which are fre-quently used in combin~tion. The alkali metal silicates usuallyhave ratios of SiO2:Na20 in the range of 0.66:1 to 4:1, ratios between 2.3:1 and 3.45:1 being generally preferred. The pre-ferred SiO2:Na20 ratio for a given case also depends on the desired degree of the contribution of the alkali metal silicate .~ .
i~ toward the alkalinity of the detergent or bath liquor. Thus it : `
- is possible that ratios between 1:1 and 2.3:1 can be especially ~ ~!
desirable, also.
The other materials used according to the invention and for the tensides, foam inhibitors, foam stabilizers.bleaches and ~;l 30 stabilizers suitable for the process according to the invention ` and/or activat~rs for theseJ as well as soil carriers, e~zy~s ahd-b~i~hten~s, are further deæcribed i~ the previously-filed ' '' .... .. . . . .
.. ~ . . . ..

lns~s8 applications S.N.197J628 and l9B,560 , wherein the above-mentioned classes of compo~nds were discuæsed in detail.
Of particular practical interest are the materials ac-cording to the invention that are powdered or granular and can be prepared according to all known technological processes The use of the compounds of for~ula I in the form o~ agglomerates can be advantageous to facilitate the finishing and handling of the products. It is generally desirable if these agglomerates break down, e.g. with reversion into the primary particles, during use.
The aluminosilicates in powder form, for example, can be ~ixed with the other components of the detergents in a very simple manner, by spraying oily orpastelike products such as nonionics on the pow-der. Another ~anner of preparation is the working of the powdered aluminosilicates into the other components of the material,which are in the form of an aqueous paste that is then turned into pow-der by crystallization processes or by drying the water with heat.
After drying in hot air, e.g. on belts or in spray-drying ovens, substances that are sensitive to heat and moisture such as bleach components and activators for theæe, enzymes, antimicrobial agents, etc. can be mixed in.
The co~position of typical textile washing agents to be use~ in the temperature range of 50 to 100C fall in the range of the following recipe:
5% to 30% of anionic and/or non-ionic and/or a~pho-teric surface-active compounds, 5% to 70~ of aluminosilicates (related to A~), 2~ to 45% of the sequestering agents for calcium ac-cording to the invention, O to 50% of wa~h alkalies not capable of sequestra-~o tion (alkaline builder salts), ; O to 50~ of bleaches as well as other additives mostly contained in detergents in small quantities.

' "`

.. . . ., . . . . ~

- - 105~658 The ~nrface-active com~oullds or tensides contain in the molecule a~ least one hydrophobic organic moiety and one water-solubilizi~ngt anionic, non ionic or amphoteric group.
The hydro~hobic moiety is mostly an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and particularly 12 to 1~ carbon atoms or an alkyl aromatic radical, such as alkyl-phenyl, with 6 to 18, preferably 8 to 16 aliphatic carbon atoms.
~ .mong the anionic surface-active compounds are, for example, soaps of natural or synthetic, preferably saturated, fatty acids, optionally, also, soaps of resinic or naphthenic acids. Suitable synthetic anionic tensides are those of the type of the sulfonates, sulfates and synthetic carboxylates.
Suitable anionic tensides of the sulfonate type are alkylbenzene sulfonates (Cg 15 alkyl) mixtures of alkene-sulfonates and hydroxyalkanesulfonates, as well as alkane-disulfonates, as they are obtained, for example, from mono-olefins with terminal or non-terminal double bonds by sulfonation ' with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkane-sulfonates which are obtained from alkanes by sulfochlorination ' or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Other suitable tensides of the sulfonate type are the esters of -sulfofatty acids, for `I example, the a-sulfonic acids of hydrogenated methyl or ethyl , esters of coconut, palmkernel or tallow fatty acids.
, Suitable tensides of the sulfate type are the sulfuric acid monoesters of primary alcohols (e.g., from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Also suitable are sulfated fatty acid 30 alkanolamides, sulfated fatty acid monoglycerides or sulfated reaction prodvcts of 1 to 4 mols of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

cb/ - 25 - .

r~J ! , . ~ .. .

lOS,'~ ;58 Ot:!~ei suit~ble anio~lic ~ensides are th~ fatty acid ~ste~s or amide~ o~ hy~oxy~ or amino-carboxylic ac.ids or sul-fonic acids, such as the fatty acid sarcosides, fatty acid glycolates, fat~y acid lactates, fatty acid taurides or fatty acid isoethionates.
The anionic tensides can be present in the form of theix alkali metal salts, such as the sodi~lm or potassium salts, the ammor.ium salts, as well as soluble salts of organic bases, such as the lower alkylolamines, for example, mono-, di- or triethanol amine.
Suitab].e non-ionic surface-active compounds or ten-sides are the addition products of 4 to 40, preferably 4 to 20 mols of ethylene ox.ide to 1 mol of a fatty alcohol, alkyl-phenol, fatty acid, fatty amine, fatty acid amide or alkane-sulfonamide. Particularly important are the addition products of 5 to 16 mols of ethylene oxi.de to coconut fatty alcohols or tallow fatty alcohols, to oleyl alcohol or to secondary alkanols , with 8 to 18, preferably 12 to 18 carbon atoms, as well as ~I monoalkylphenols or dialkylphenols with 6 to 14 carbon atoms j 20 in the alky].s. In addition to these water-soluble non-ionics, polyglycol ethers with 1 to 4 ethylene glycol ether radicals ;-~ in the molecule, which are insoluble ornDt completely water-, soluble are also of interest, particularly if they are used to-~ gether with water-soluble non-ionic or anionic tensides.
.; .
Furthermore, the water-soluble addition products of 20 to 250 mols of ethylene-oxide to polyoxypropylene glycol , containing 10 to 100 propylene glycol ether groups (Pluronics ), to alkylene diamine-polyoxypropylene glycol (Tetronics `!
:~ ~ ), and to alkylpolyoxypropylene glycols with 1 to 10 carbon `

atoms in the alkyl cnain, can also be used where the poly-oxypropylene glycol chain acts as a hydrophobic radical, Non-ionic tensides of the type of the amine oxides or sulfoxides can also be used.

~, .
` cb/ - 26 -105;~658 The ~oamin~ power o~ ~he tenside can ~e increased ox reduced by combination of suitable tenside types. A re-duction can also be achieved by additions of non surface-active or~anic substances.
Suitable foam stabilizers, particularly in tensides of the sulfonate or sulfate type, are surface-active carboxy or sulfobetaines, as well as the above-named non-ionics of the alkylolamide type. Moreover, fat~y alcohols or higher terminal diols have been suggested for this purpose.
A reduced foaming power, that is desixable for the use in washing machines, is often attained by combination of different tenside types, such as of sulfates and/or sulfonates with nonionics, and/or with soaps. In soaps, the foam inhibi-tion increases with the degree of saturation and the number ' of carbons in the fatty acid residue. Soaps derived from saturated C20_24 fatty acids have been proven good as foam inhibitors.
The non-tenside foam inhibitors included N-alkylated aminotriazines, optionally containing chlorine, which are obtained by the reaction of 1 mol of cyanuric acid chloride ~ith 2 to 3 mols of a mono- and/or dialkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl radicals~ Similar-ly effective are propoxylated and/or butoxylated aminotriazines, such as, products that are obtained by the addition of from . 5 to 10 mols of propylene oxide to 1 mol of melamine and further addition of from 10 to 50 mols of butylene oxide to ~ 27 this propylene-oxide derivati~e.

::

cb/ - 27 -:, 105'~ 58 I.ikewis~ sui~a~le as non-~el-side foam inhibitors are water-insoluble orqanic compounds, like paraffins, or halogenated par~ffins with melting points below 100C, ali-phatic C18 to C40 ketones, as well as aliphatic carboxylic acid esters which contain in the acid or alcohol residue, optionally, also in both of these residues, at least 18 carbon atoms (such as triglycerides or fatty acid/fat~y alcohol esters).
These compounds can be used to redu_e foaming, particularly in combinations of tensides of the sulfate and/or sulfonate type with soaps.
Particularly low-foaming non-~onics, which can be used either alone or in combination with anionic, amphoteric and non-ionic tensides, and which reduce the foamlng power of high-foaming tensides, are the addition products of propylene oxide on the above-described surface-active polyoxyethylene-glycol ethers as well as the likewise-described addition pro-ducts of ethylene oxide to polyoxypropylene g]ycols and to alkylenediamine polyoxypropylene glycols or to alkyl poly-19 oxypropylene glyools having 1 to 10 carbons in the alkyl.

, , .

.
: . . .

~ c~ - 28 -- 1~)5~658 Weakly acid, neutral or alkaline-reactirlg inorganic or or~anic salts can be used as builder salts.
Suitable weakly acid, neutral or ~lkaline-reacting salt:s for use according to the invention are, for example, the bicarbonates, carbonates, borates or silicates of the alkali metals, alkali metal sulfates, as well as the alkali metal salts of organic, non-surface-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing from 1 to 8 carbon atoms. These include, for example, water-soluble salts of benzenesulfonic acid, toluenesulfonic acid or xylene-sulfonic acid, water soluble salts of sulfoacetic acid, sulfobenzoic acid or of sulfodicarboxylic acids.
The compounds mentioned above as sequestering or precipitating agents for calcium are suitable as builder salts.
They can, therefore, be present in the agents according to the invention in larger quantities than is necessary to per-form their function as sequestering or precipitating compounds for calcium.
The individual components of the products used pre-~, 20 ferably as textile washing compositions, or as household clean-- Lng compositions, particularly the builder salts, are mostly so selected that the preparations react neutral to strongly ; alkaline, so that the pH-value of a 1% solution of the prepara-tion is mostly in the range of 7 to 12. Fine washing agents show mostly a neutral to weakly alkaline reaction ~pH value = 7 to 9.51, while soaking agents, prewashing agents and boiling washing agents are more alkaline (pH value = 9.5 to 12, pre-ferably 10 to 11.5). If higher pH-values are required for special cleaning purposes, these can be easily obtained by using alkali metal silicates of a suitable Na2O:SiO2 ratio or caustic alkalies.

.
:' cb/ - 29 -.~ .

" 1()5'~{~58 ~ mong the compowlds ~rving as bleaching agents and releasinq il2O2 il~ water, soclium per~oratc tetrahydrate ~NaBO2.
! H2O3 . 3 H2O) and the monohydrate (~aBO2 ~l2O2) ar~ of parti-cular importance. But also other ~22 releasing borates can also be used, such as perborax Na2E4O7 . 4 H2O. These com-pounds can be rep]aced partly or completely by other carriers of active oxygen, particularly by peroxyhydrates such as peroxycarbonates, (Na2CO3 . 1.5 ~f22), peroxypyrophosphates, citrate perhydrates, urea-E12O2 compounds, as well as by H2O2-releasing peracid salts, such as Caroates (KHSO5), per~enzoates or peroxyphthalates.
It is recommended to incorporate water-soluble and/
or water-insoluble stabilizers for the peroxy compounds to-gether with latter in amounts of 0.25% to 10~ by weight.
Water-insoluble stabilizers, which amount to 1~ to 8%, pre-ferably 2~ to 7~ of t~e weight of the entire preparation are, ~ for example, the magnesium having MgO : SiO2 ratio of 4:1 to .J 1 4, preferably 2:1 to 1:2, and particularly l:l, which are mostly obtained by precipitation from a~ueous solutions. In their place, other alkaline earth metal, cadmium or tin silicates of corresponding compositions are also useable.
Also hydrous oxides of tin are suitable as stabilizers, Water~soluble stabilizers, which can be present together with ~ water-insoluble stabilizers, are mostly the sequestering ; agents`which can be added in amounts of 0.25% to 5%, preferably 0.5% to 2.5~ of the weight of the entire preparation. In p~rticular, these are the organic sequestering agents which show a pronounced complexing power fox heavy metal ions, such as for example, the alkali metal salts of ethylenediamine-tetraacetic acid, nitrilo-trimethylenephosphonic acid l-hydroxyethane l,l-diphosphonic acid, .
.
cb! - 30 -1~5;~658 In orde~ to obtain a satis~actory blcachin~ effect ~ en washin~3 at ~empcratures below 80C, particularly in the rangle of 60~ to 40C, activator-containing bleaching components are preferably incorporated in the preparations.
Certain ~J-acyl and/or O-acyl compounds forming, with H2O2, organic per acids serve as activators for per compounds releasing }12O2 in water. Particularly to be mentioned are acetyl, propionyl or benzoyl compounds, as well as carbonic ; acid or pyrocarbonic acid esters. Suitable compounds are among others: the N-diacylated and N,N'-tetraacylated amines, such as N, N, N', N'-tetraacetyl-methylenediamine, N,N,N',N'-tetraacetyl-ethylenediamine, N,N-diacetyl-aniline and N,N-diacetyl-p-toluidine, or the 1,3-diacylated hydantoins and alkyl~N-sulfonyl-carbonamides, such as N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesy -p-nitrobenzamide,.and N-methyl-N-mesyl-p-methoxybenzamide, the N-acylated cyclic hydrazides, acylated triazoles or urazoles, such as monoacetyl maleic acid hydrazide, the O,N,N-tri-substituted hydroxylamines, such as O-benzoyl-N,N-succinyl-hydroxylamine, O-acetyl- N, N-succinyl-hydroxylamine, O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine, O-p-nitro-benzoyl-N,~-succiAyl-hydroxyllmine ~nd , . .

.

; cb~ - 31 -105;~658 O,l~,N-triacetyl-h~-droxyl.~Mine, the N,N'-di.acyl-sulfuryl-amides, such as N,N'-dinle~ilyl--N,N'-diacctyl-sulfurylamid~ and N,N'-diethyl-N~N'-dicthyl-N,~I'-dipropionyl-sulfuryl amide, the tri-acyl cyanurates, such as triacetyl cyanurate or tribenzoyl cyanurate, thc carboxylic acid anhydrides, such as benzoic acid anhydride, m-chlorobenzoic acid anhydride, phthalic acid anhydride, 4-chlorophthalic acid anhydride, the sugar esters, such as glucose pentaacetate, the 1,3-diacyl-4,5-diacyloxyimid-azolidines, for example the compounds 1,3-diformyl-4,5-di-acetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine, the acylated glycolurils, such as tetrapropionyl glycoluril or diacetyl-di-' benzoyl glycoluril, the diacylated 2,5- diketopiperazines, : such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-3,6-dimethyl-2,5-diketo-piperazine, the acetylated or benzolylated products of propy-lene-diurea or 2,2-dimethyl-propylene diurea [2,4,6,8-tetraaza- :
~'~ bicyclo-(3,3,1)-nonane-3,7-dione or its 9,9-dimethyl derivative~
. ànd the sodium salts of p-ethoxycarbonyloxy)-benzolc acid and p-(propoxycarbonyloxy)-benzene sulfonic acid.
', .

. .
'`'~' .

:

.

., .

:" . .
"
'~
~b/ - 32 -.. , , , . , . _ . .. . .. , . .. . . , . ~ . . . . .

lOS~658 The activated chlorine compow~ds serving ~s bleach-in~ aqents can be o~ an inorganic or or~anic nature.
The inorganic active chlorine compounds include alkaline metal hypochlorites, which can be used particularly in the form of their mixed salts or addition compounds with orthophosphates or on condensed phosphates such as with alkali metal pyrophosphates and polyphosphates, or with alkali metal silicates. If the washing agents and washin~ assistant com-positions contain mono-persulfates and chlorides, active chlorine is formed in aqueous solution.
The organic active-chlorine compounds which can be used are particularly the N-chloro compounds, where one or two chlorine atoms are linked to a nitrogen atom, the third valence of the nitrQgen atoms leading preferably to a negative group, particularly to a CO- or SO2-group. These compounds include dichlorocyanuric acid and trichlorocyanuric acid or their salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.
The preparations according to the inVention can furthermore contain soil suspension agents or dirt carriers, which keep the dirt released from the fibers in suspension in ` the li~uor and so prevent graying. Suitable compounds are ~ater-soluble colloids, mostly of an organic nature, such as the water-soluble saits of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic :1j ;~ acids of starch or cellulose, or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides con-taining acid groups are also suitable for this purpose. Further-~ - more, soluble starch preparations and other than the above-; 30 mentioned starch products can be used, for example, degraded starches, aldehyde starches etc. Polyvinyl pyrrolidone can ; also be used.
. ' ' .
cb/ 33 .

" lOS'~:6S8 The ellzy~e prc~ara~ions to be used are mostly a mixture of enzymc.s Wit~l different effects, such as pro-tcases, carbohydr~ses, estexases, lipases, oxidoreductases, catalases, peroxidases, uxeases, isomerases, lyases, trans-ferasos, desmolases, or nucleases. Of particular interest are the enzymes, obtained from bacteria strains or from fungi, such as Bacillus subtilis or Streptomyces griseus, particularly proteases and amylases, which are relatively stable towards alkalis, percompounds, and anionic tensides and are still effective at temperatures up to 70C.
- Enzyme preparations are marketed by the manufacturers mostly as a~ueous solutions of the active substances or as powders, granulates or as cold-sprayed products. They fre-quently contain sodium sulfate, sodium chloride, alkali metal ortho-, pyro~ and polyphosphates, particularly tripolyphosphate, -~ ~-as fillers. Dust-free preparations are particularly valued.
' These are obtained in a known manner by incorporating of oily ~ or pasty Nonionics or by granulation with the aid of melts of J water-of-crystallization-containing salts in their own water-of-crystallization.
;, .
, Enzymes may be incorporated which are specific i for certain types of soil, for example, proteases or amylases ` or lipases. Preferably~ combinations of enzymes with differ-` ent effects are used, particularly combinations of proteases : ,. .
~ and amylases.
.. . .
, .

i ::

. . .
. . . .
' ' ,; ~-.

- cb~ - 34 -105;~658 The washin~ a~ents can contain optical brighteners such as those for cotton, particularly derivativ~s of diamino-stilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1, 3~5-triazin-6-yl-amino)-stilbene-2,2'-disulfonic acid or simil~rly compounds which have instead of the morpholino group, a diethanolamino group, a methylamino group or a 2-methoxy-ethylamino group. ~righteners for polyamide fibers which can be used are those of the type of the 1,3-diaryl-2-pyrazolines, for example, the compound 1-(p-sulfamoylphenyl)-3-(p-chlorophenyl)-2-p~razol;ne, as well as compounds of similar composition which have instead of the sulfamoyl group, for example, the methoxycarbonyl group, the 2-methoxyetnoxycarbonyl ~roup, the acetylamino group or the vinylsulfonyl group.
Suitable polyamide brighteners are also the substituted aminocumarins, for example, 4-methyl-7-dimethylamino-cumarin or 4-methyl-7-diethylaminocumarin. Furthermore, the compounds 1-~2-benzimidazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)-ethylene and l-ethyl-3-phenyl-7-diethylamino-carbostyril can also be used as polyamide brighteners. Brighteners for poly-ester and polyamide fibers which can be used are the compounds 2,5-di-~2-benzoxazolyl)-thiophene,2-(2-benzoxazolyl)-naphtho-12,3~b~-thiophene and 1,2-di-(5-methyl-2-benzoxazolyl)-ethylene.
~urthermore, brighteners of the type of the substituted 4,4'-`distyryl-diphenyls can be utilized, for example, the compound 4,4'-bis-~4-chloro-3-sulfostyryl)-diphenyl. Mixtures of the above-mentioned briqhteners can likewise be used.

`

cb/

,, " , . , .. . , , ~ . ~ . ~ .. . . . . . . . . . . . . .. .

1 05'~658 The following spcci~ic eml~odiments are illustrativ~
of the invention with~ut ~eing limitativ~ in any respect.
E X ~ M P L E S
First~ the production of the finished alumino- -silicat~s is described, for which no invention is claimed.
Oth~r aluminosilicates useful in the inven~ion are described in the first filed S.N. 197,~28.
^- PROCESS CONDITIONS
.
The alun~inate solution, diluted with deionized water was mixed in a vessel of 15 liter capacity, under vi~orous stirring with the silicate solution. Both solutions were at xoom temperature. An X-ray amorphous sodium aluminosilicate ~; was formed in the exothermic reaction as a primary precipita-tion product. After stirring for io minutes, the suspension of the precipitation product was either separated as an amor-phous product or transferred to a crystallization vessel where it remained for some time at the elevated temperature given to crystallize. After draining off the liquor from the crystals ' and washing with deionized water until the outflowing wash water had a pH-value of about 10, the filter residue was dried.
When there is any deviation from this general production pro-cedure, this is mentioned explicitly in the specific part.

Thus, for example, in some cases for the practical tests, the homogenized uncrystallized suspension of the prec1pitation .. ; .
product or the crystal sludge was used. The water content was determined by heatinq the product for one hour to 800~.
In 'the production of microcrystalline aluminosili-cates, indicated by the suffix "m", the aluminate solution , diluted with deionized water was mixed with the silicate solu-, tion and mixed in a high-speed intensive stirxer ~10,000 rpm, ~'Ultxaturrax", made by Janke 6 Kunkel IK~-Werk, Stauffen/

Breisgau-Federal Republic of Germany). After vigorous stirring ' ~ cb/ - 36 -~ .

~05'~658 or 10 minutes, the suspension of the amorphous precipitation product was transferred to a crystallization vessel where the formation of large crystals was prevented by stirring the suspension. After draining off the liquor and washing with deionized water until the outflowing water had a pEI ~alue of about 10, the filter residue was dried, then ground in a ball mill and separated in a centrifugal sifter ~"Microplex" air sifter, made by Alpine, Augsburg, Federal Republic of Germany) into two fractions, of which the finer fraction contained no portions above 10 ~. The particle size distributio~ was determined by means of a sedimentation scale.
The degree of crystallization of an aluminosilicate can be determined from the intensity of the interference lines of an X-ray diffraction diagram of the respective product, compared to the corresponding diagrams of X-ray amorphous or fully crystallized products.
~ All data in % are in percent by weight.
; The calcium binding power of the aluminosilicates or borosilicates was determined in the following manner.
liter of an aqueous solution, containing 0.594 gm of CaC12 ~= 300 mg CaO/l = 30dH) and adjusted to a pH of 10 with diluted NaOH, was mixed with 1 gm of the aluminosilicate or borosilicate (on the anhydrous basis, AS). Then the suspension was stirred vigorously for 15 minutes at a temperature of 22C (+ 2C).
....
` After filtering off the aluminosilicate, the residual hardness x of the filtrate was determined. From it, the calcium binding power was calculated in mg CaO/gm. ~s according to the formula:
(30 - x~ . 10.
If calcium binding powex is determined at higher tem-perature, for example, at 60C, better values are obtained than : ` .

.
,.'' .
cb/ 37 105'~658 at 22C. This f~ct distin~uishes the aluminosilica~es from most of the soluble sequestering ayents that have been suggested so ~ar for use in detergents and represents a particular technical progress in their use.
Producti.~n conditions for aluminosilicate I;
:~:
Precipitation: 2.985 kg of an aluminate solution of the composition: 17.7% Na2O, 15.8% A12O3, 66.6~ ~.

0.15 kg of sodium hydroxide 9.420 kg of water 2.445 kg of a 25.8% sodium silicate solu-: tion of the composition l Na2O. 6.0 :
SiO2, prepared freshly from commercial waterglass and easily alkali-soluble silica Crystallization: 24 hours at 80C
Drying: 24 hours at 100C
1 Composition: 0.9 Na2O . 1 A12O3 . 2.05 SiO2 . 4.3 H2O ~:
' ~ (= 21.6% H2O~
Degree o~ crystal-lization: Fully cr~stalline ,~ Calcium binding c~ power: 150 mg CaO/gm AS.

If the product obtained was dried for 1 hour at 400C, an aluminum sil~cate Ia was obta~ned of the compositio~:
.; .
0,9 Na2O , l A12O3 . 2.04 SiO2. 2.0 H2O (= 11.4%

~,~ H2OL which is l~kewise suita~le for the purposes of the nvention.

Product conditions for aluminosilicate II:

Precipitation: 2.115 kg of an aluminate solution of the ' 30 compoSition: 1~.7% Na20 15.8~ A1203 0.585 kg of sodium hydroxide .
~ cb! - 38 -.. . . . . . ~ .. ~ . . . . . .. . . . .

105'~658 9.615 kg of water 2.685 kg of a 25.8~ sodium silicate solution of the composition: 1 Na20. 6 sio2 (pre-pared as under I) Crystallization: 24 hours at 80C
Drying: 24 hours at 100C and 20 torr.
Composition: 0.8 Na2O. 1 ~12O3. 2.655 SiO2. 5.2 H2O
- Degree of crystallization: Fully crystalline Calcium bi~ding - power: 120 mg CaO/gm AS.

This product too can be dehydrated by drying ~for 1 hour at 400C) to the composition:

0.8 Na20 1 A 2 3 2 2 This dehydration product IIa is likewise suitable for the purposes of the invention.
The aluminosilicates I and II show in the x-ray diffraction diagram the following interference lines.
d- values, recorded with Cu-K~- radiation in A
I II
_ 14.4 .i. .
12.4 8.8 8.6 ` 7.0 _ 4.4 ~+~

4.1 ~+i ~ 3.8 (+) 3.68 ~+~

3.38 ~. .
..

~/ - 39 -.

- i~S'Z658 3.26 (+) 2.96 (+) - 2. 8~3 (+) ~ 2.79 (+) 2.73 (+) ~ 2.~6 (+) 2.60 (+) - ` `~
.
It is quite posaible that not all these interference lines wlll appear in the X-ray diffraction diagram, particularly 10if the aluminosilicates are not fully crystallized. For this : .
.~ reason, the d-values which are the most important for the characterization of the~e types are identi~ied by a "(~
Production conditions for aluminosilicate Im Precipitation: 2.985 kg of an aluminate solution of the ;
composition 17.7% Na20, 15.8~ A1203, ~.
''~ 66-6% H20 0.150 kg of sodium hydroxide ~` 9.420 kg of water 2.445 kg of a 25.8~ sodium ~ilicate solution ~; 20 o~ the composition: 1 Na20. 6 SiO2 (prepared a~ in I) Cry tallization: 6 hours at 90C
Drying: 24 hours at 100C
Composition: -9 Na2 1 A1203 . 2.04 SiO2 . 4.3 H20 21.6~ H20) ~ ., Degree of Crystal-lization: Completely crystalline i Caleium blnding `i power : 170 mg CaO/gm AS.

. "

~I

~ -40-~:i ~S~iS8 The distribution of the particle size determined by sedimentation analysis was in the following range: -> 40_u = 0~ The ~ax~um range of the lO u - 85~ to 95~ particle size distribution 8,u - 50% to 95~ curve was situated at 3 to 6~u.
The degree of crystalllzation of an aluminum silicate can be determined from the intensity of the interference lines of an x-ray diffraction diagram of each product in comparison 10 with the res~ ctive diagrams of amorphous or completely crystal- -lized products.
The salt constituentæ contained in the detergents of the examples, æuch as surfactants in salt form, other organic salts, as well as inorganic salts, were present as sodiu~ salt, unless ; e~plicitly stated otherwise. This also applies to the precipita-tion inhibitors or chelating agents which are d~slgnated for sinplicity's sake as the corresponding acids. The designatlons and abbreviatlons used have the following meaning:
ABS the salt of alkylbenzenesulfonic acld wlth 10 to 15, ;
preferably 11 to 13 carbon ato~s in the alkyl chain, obtained by condensation of straight-chain olefins with benzene and sul-fonation of the alkylbenzene thus obtained.
Fs-Ester Sulfonate a sulfonate obtained by sulfonation with S03 of a methyl ester of a hardened tallow fatty acid.
` Olefin Sulfonate a sulfonate, obtained by the sulfonation with S03 of ~ixtures of straight-chain, non-ter~inal olefins with 12 to 18 carbon atoms and hydroly~ation of the sulfonation product with caustic, which consists mainly of alkene sulfonate and hydroxy alkane sulfonate, but contains also s~all amounts of 3o alkane disulfonates.
OA + x EO or TA + x EO the addition products of ethylene oxide (EO) to technical oleyl alcohol (OA) or to tallow fatty ~ -41 :.., 105'~5~ :
alcohol (~A) (lodine number = 0.5), where the values for x indi- -cate the molar amount of ethylene oxide added to 1 mol ofalcohol.
TA-Sulfonate the salt of a sulfated, mainly saturated fatty alcohol, produced by reductlon of tallow fatty acid.
CMC the salt of carboxymethyl cellulose.
Perborate a product of the approximate composition NaB02 . H202 . 3 H20, containing appro~imately 10~ active oxygen.
Foam Inhibitor an N-alkylated aminotriazine obtained by the reaction of cyanuric chloride with a mono- or dialkylamine with 8 to 18 carbon atoms in the alkyl.
Aluminosilicate a microcrystalline aluminosilicate Im prepared as described above, where the percentages refer to the ~- proportion by weight of the anhydrous active substance (AS).
Na-Sillcate a ~odium silicate with a SiO2:Na20 ratio of , 3,35:1 by weight.
Soap C12 -C22 or Soap C16 -Cla salts of fatty acids with - the given number of carbon atoms, EDTA the salt of ethylenediaminetetraacetic acid , .
PHAS the salt of poly-(a-hydroxyacrylic acid), nanufac-turer; Solvay & Cie,- Belgium; molecular weight in the range of 100,000 to 150,000.
Citric Acid Pyrolyzate a product of the pyrolysis of -` citric acid having an average of four carboxyl groups, in the ~, form of the product of pyrolysis, prepared as described above and reacted with sodium bisulfate. Manufacturers Citrex S.A., ~- Belgium.
~-` Allyl Acetate~MSA a linear 1:1 copolymerizate of allyl acetate and ~aleic acid anhydride, where the maleic acid anhy-dride groups are hydrolyzed. Molecular weight in the range of 4,000 to 10,000.
~' : -~()S;~t~5~

Yinyl Meth~l Ether~MSA a copolymerizate in which vinyl met;hyl ether and hydrolyzed units of maleic acid are present at a ratio of 1:1; molecular weight 250,000, Several representative recipes for detergents according to the invention are ~ollowing.

Component~ Example 1 Soap C12 -C22 3 OA + 5 EO 3.
Oxoalkohol C12_15 + 7.EO ~ 8.0 CMC 1.5 EDTA 0,2 Mg SiO3 1.5 Optical brightener o.3 Aluminosilicate 30.0 Sodium silicate 4.0 Citric acid pyrolyzate 10.0 Remainder Na2S04 + H20 ,, ' Components Example 2Example 3 Olefinsulfonate 8.0 5.0 TA-sulfate _ 2.0 soaP C16-C18 2.0 2.5 OA + 10 EO - 4.0 i CMC 1.5 1.5 EDTA 0.2 0,2 Mg SiO3 1,5 1,5 Optical brightener 0.3 0.15 Foam inhibitor 1.0 1.0 Perborate 30.0 25.0 Aluminosilicate 27.0 20.0 Sodium carbonate 7.0 10.0 -:

lOS;~i58 Co~]?onents Example 2 Example 3 Na-l3ilicate 7,0 10.0 Vinylrnethylether/MSA 10. 0 Cit:ric acid pyrolyzate - 8,0 Re~ainder Na2S04 + H20 Allyl acetate/MSA was used with the same success instead of vinyl methyl ether/MSA in E~ample 2.

Components Examples ABS 8.0 - - -Oleflnsulfonate - 8.0 Fs-Esteræulfonate - - 7.0 Soap C12-C22 4-: Soap C16-ClB 2.0 3.0 TA + 5 EO 1.5 - - , TA + 14 EO 2.5 OA + 5 EO - - - 3.0 Oxoalkohol C12_1s + 7 EO - 3.0 3.0 8.0 CMC 1.5 1.5 1.5 1.5 EDTA 0.2 0.2 0.2 Q.2 Mg SiO3 1.5 1.5 1.5 1.5 Optical brightener 0.15 0-3 0.15 0-3 Foam inhibitor - 1.0 0.5 Perborate 25.0 30,0 20,0 : Aluminosilicate 25.0 30.0 15.0 8.0 Sodium carbonate - 7.0 15.0 12.0 Na-silicate 15.0 7' 2.5 13,0 l-hydroxy-l-phenylmethan-i diphosphonic acid 6.o ~ 30 l-amino-p;chlorphen~l-; methandiphosphonic acid - 4.0 1(~5;~;S8 Components Exa~ples ~ 5 6 7 3-a~nino-1-hydroxypropane~
:L-diphosphonic acid - - 4.0 2-11ydroxy-2,7-dioxo-3-a:nino-3-phosphonyl-1, 2-azaphosphacycloheptane - - - 10.0 ; Remainder Na2S04 + water Azacycloheptane-2,2-diphosphonic acid or pyrrolidone-2,2-diphos-phonic acid was used in the same amount and with the sa~e effectinstead Or 2-hydroxy-2,7-dioxo-3-a~ino-3-phosphonyl-1,2-aza-.~ phosphacycloheptane, Also l-hydroxy-p-chlorophenylmethane di-phosphonic acid instead o~ l-hydroxy-l-phenyl-methane diphos-phonic acid and l-amino-l-phenylmethane diphosphonic acid instead -.~ of l-amino-p-chlorophenylmethane diphosphonic acid was employed ..-.
in the sa~e amount and with the same ef~ect, , Components Examples .~ 8 9 Soap Cl2-c22 2,0 3.0 TA + 5 EO 3.
TA + 14 EO 7,0 ~ . , OA ~ 5 EO - 3,o Oxoalkohol C12_15 + 7 EO ~ 8.0 CMC 1,5 1.5 .. EDTA 0,2 0.2 ~:"
Mg SiO3 1.5 1.5 .' Optical brightener 0.25 0.3 Perborate 30, o Aluminosilicate 15.0 8,0 : 3 Sodium carbonate 20,0 12.0 ` Na-silicate 15.0 13.0 Vinylmethylether/MSA - 12.0 PHAS 15,0 . -45-, 1(~5A~658 Co~lponents Exa~ples Re~lainder Na2S04 + H20 Components Exa~ples ABS - 8,0 Olefinæulfonate 8.0 Soap C12-C22 soaP C16-C18 2.0 TA + 14 EO _ 3 0 Oxoalkohol C12_1s + 7 EO
CMC 1.5 1.5 EDIA 0,2 0,2 Mg SiO3 1.5 1.5 Optical brightener o,3 0.15 Foam inhibitor 1.0 0.4 Perborate 30.0 25.0 Aluminosilicate 30.0 25.0 Na-~ilicate 3.0 15.0 . 20 Citric acid pyrolyzate 10. 0 7. 0 Rema inder Na2SO~ = H20 . Components Example 12 soap Cl2-c22 2.0 - TA ~ 5 EO 3.0 : TA + 14 EO 7.0 CMC 1.5 EDIA 0.2 Mg SiO3 1~5 Optical brightener 0.25 Perborate 20.0 -46_ 1~5'~58 Co~ponents Example 12 Alwninosilicate 15.0 Sodium carbonate 20.0 ~a-silicate 15.0 l-chloro-l-phenylmethanediphos-phonic acid 8.0 Remainder Na2S04 + H20 In Examples 4, 8 and 12, the combinations o~ the aluminosilicate and polyphosphonate compounds are combined with the particularly advantageouæ nonlonic surface-active compound combinations, where nonionic compounds with 8 to 20 ethylene glycol units in the molecule are combined with nonionic compounds containing 2 to 6 ethylene glycol units per molecule, optionally, with anionic surface-active compounds added to the nonlonic compounds.
The ma~ority of the given recipes, and ~11 those con-taining Perborate, is intended for use as so-called complete detergents for high temperature or boiling washing (approx. 95C), whereas the recipes without Perborate are for washing at inter-mediate temperatures, such as about 60C. However, the deter-23 gents without Perborate may be used success~ully also at higher : temperatures, or as detergents for ~ine washables. Detergents ~or fine washables according to the invention usually have a hlgher proportion of tenside in the invention than the complete detergents described in the examples.
A detailed description of the preparation of the deter-gents according to the invention was omitted, æince they can be ; prepared according to procedures well-known in the technology.
The preceding speci~ic embodiments are illustrative of the practice o~ the invention. It is to be understood, however, that other expedient known to those skilled in the art or dis-closed hereinJ may be employed without departing from the spirit o~ the invention or the scope of the appended claims.

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process of treating soiled textiles by con-tacting soiled textiles with an aqueous liquor containing at least two compounds inhibiting alkaline earth metal ion precipitation on said soiled textiles as well as optionally at least one surface-active compound for a time sufficient to disperse or dissolve the soil from said soiled textiles into said aqueous liquor, separating said aqueous liquor and recovering said textiles substantially soil-free, comprising using (1) from 0.2 to 10 gm of anhydrous active substance per liter of at least one finely-dispersed, water-insoluble silicate compound containing at least some combined water and having primary particles in the size range of from 100µ to 0.01µ , a calcium binding power of from 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2O)x . Me2O3 . (SiO2)y where M is a cation selected from the group consisting of sodium, lithium, potassium and ammonium, x is a number of from 0.7 to 1.5, Me is a member selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, and (2) from 0.05 to 2 gm per liter of at least one water-soluble compound selected from the group consisting of the free acid and acid salts of cations exchangeable with calcium of the following acids:
A) An azacycloalkane-2,2-diphosphonic acid having the formula wherein m is an integer from 3 to 5 and R3 is selected from the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms, B) A cyclic aminophosphonic acid having the formula wherein p is an integer from 1 to 3 and R1 is selected from the group consisting of hydrogen and alkyl having 1 to 6 carbon atoms, C) Pyrrolidone-5,5-diphosphonic acid and N-alkyl-pyrrolidone-5,5-diphosphonic acid where alkyl has from 1 to 6 carbon atoms, D) A copolymerizate of an ester of an alkenol having from 3 to 6 carbon atoms with a lower alkanoic acld with a maleic compound selected from the group consisting of maleic acid and maleic acid anhydride in substantially a 1:1 ratio, where any anhydride groups are predominantly hydrolyzed to acid groups, E) Poly-a-hydroxyacrylic acid with a molecular weight of at least 20,000, F) A copolymerizate of a vinyl-lower alkyl ether with a maleic compound selected from the group consisting of maleic acid and maleic acid anhydride in substantially a 1:1 ratio, where any anhydride groups are predominantly hydrolyzed to acid groups, G) 3-amino-1-hydroxypropane-1,1-diphosphonic acid, H) A polyphosphonic acid having the formula wherein X is a member selected from the group consisting of OH and NH2 and Y is a member selected from the group con-sisting of hydrogen and halogen, with the proviso that when X is NH2, Y is halogen, and I) A citric acid pyrolyzate having at least 4 carboxyl groups per molecule and at least one olefinic-unsaturation, and the bisulfite addition product thereof;
wherein the ratio of said water-soluble compared to said silicate compound in said aqueous liquor is from 1:8 to 2:1.

2. The process of claim 1 wherein, in said formula for said silicate compound, x is a number from 0.7 to 1.1 and y is a number from 1.3 to 3.3.

3. The process of claim 1 wherein said silicate compound is crystalline.

4. The process of claim 1 wherein said at least two compound inhibiting alkaline earth metal ion precipitation are employed in an amount whereby the residual hardness of said aqueous liquor is from 0.5° to 3°dH.

5. Washing auxiliary compositions consisting essentially of (a) at least one water-soluble compound capable of inhibiting the precipitation of alkaline earth metal ions selected from the group consisting of the free acid and acid salts of cations exchangeable with calcium of the following acids:
A) An azacycloalkane-2,2-diphosphonic acid having the formula wherein m is an integer from 3 to 5 and R3 is selected from.
the group consisting of hydrogen and alkyl having 1 to 3 carbon atoms, B) A cyclic aminophosphonic acid having the formula wherein p is an integer from 1 to 3 and R1 is selected from the group consisting of hydrogen and alkyl having 1 to 6 carbon atoms, C) Pyrrolidone-5,5-diphosphonic acid and N-alkyl-pyrrolidone-5,5-diphosphonic acid where alkyl has from 1 to 6 carbon atoms, D) A copolymerizate of an ester of an alkenol having from 3 to 6 carbon atoms with a lower alkanoic acid with a maleic compound selected from the group consisting of maleic acid and maleic acid anhydride in substantially a 1:1 ratio, where any anhydride groups are predominantly hydrolyzed to acid groups, E) Poly-a-hydroxyacrylic acid with a molecular weight of at least 20,000, F) A copolymerizate of a vinyl-lower alkyl ester with a maleic compound selected from the group consisting of maleic acid and maleic acid anhydride in substantially a 1:1 ratio, where any anhydride groups are predominantly hydrolyzed to acid groups, G) 3-amino-1-hydroxypropane-1,1-diphosphonic acid, H) A polyphosphonic acid having the formula wherein X is a member selected from the group consisting of OH
and NH2 and Y is a member selected from the group consisting of hydrogen and halogen, with the proviso that when X is NH2, Y is halogen, and I) A citric acid pyrolyzate having at least 4 carboxyl groups per molecule and at least one olefinic-unsaturation, and the bisulfite addition product thereof, and (b) at least one finely-dispersed water-insoluble silicate compound containing at least some combined water and having primary particles in the size range of from 100µ to 0.01µ, a calcium binding power of from 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2O)x . Me2O3 . (SiO2)y where M is a cation selected from the group consisting of sodium, lithium, potassium and ammonium, x is a number of from 0.7 to 1.5, Me is a member selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, where the ratio by weight of said component (a) to said component (b) is from 8:1 to 1:2.