CA1058046A - Washing agent compositions including aluminosilicates and nta and processes of washing - 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 compounds inhibiting alkaline earth metal ion precipita-tion on said soiled textiles comprising using (1) 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 Me203 (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) a combination of A) a water-soluble salt exchangeable with calcium of nitrilotriacetic acid B) a calcium binding phosphate, and/or C) an alkali metal carbonate or silicate, as said compounds inhibiting alkaline earth metal precipitation, as well as washing composi-tions containing said at least two compounds.

- A -

Description

1058al46 As known, ~he deteryents used ln the household, in . . .
; commercial estnblisllments and ln lnclustry, frequently contaln large quantl~ies of condensed phosphates, partlcular]y trlpoly-phosphates. These are provlded to ~equester the hardness form-ers of tap water and are responslble to a great extent for ~ increaslng ~he cleanlng power of the caplllary-active washing ,- substances. The phosphorus content of these agents has been crltici~ed by the public in connection with questions of the ~'~ protection of the environment. The view is frequently expressed that the phosphates, which arrive in the rivers and lakes after .
treatment of the sewage, have great influence on the eutrophi-cation of the waters, and is 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 washing and cleaning.~", processes or from the agents used for this purpose, or at least to substantially reduce its proportion.
Copending, commonly-assigned Canadian Patent Appli-.~,, .
cation Serial No. 197,628, filed April 16, 1974 discloses a process for the washing, bleaching or cleaning of solid materials, particularly textiles, by treating these materials with a liquor containing compounds able to bind the cations ~` that make water hard. The process is characteriæed in that finely-dispersed, water-insoluble silicate compounds having :`, calcium-binding capacity of at least 50 mg CaO/gm of anhydrous ~1 ,;, . ..
active substance (AS) and having the formula I, combined water not shown ~" v:
(MZ/no~x Me2O3 . (SiOz)y (I) ~, where M is a cation of the ~alence n, exchangeable with calcium, x is a number 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, are suspended in the aqueous treatment bath The ~',~ , ..
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n~J ~

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process oF the pcltent rnalces poss:Lble the completc or partlal repl~lcement of phospllates that bind calcium ions by complexing and are still belng used in the washing and cleaning process.

-~. . .
The calcium binding capacity of the above-defined compounds may reach values 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 te~t, for the salce of sim-plicity This applies particularly to the sodium alumino-silicates that are to be used preferably. All data given fortheir preparation and processing apply accordingly to the ::,, , , :
totality of the above aluminosilicate 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, lithium, ~ ~ .
potassium, ammonium or magnesium9 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 more than 2 carbon atoms per alkyl radical, or not more than 3 ca~bon atoms per alkylol radical, This process is indicated as bein~ further improved in that the removal of soil is considerably improved when .,.. ; :- . .. ..
~j- another compound is employed in the liquor which has a sequester- ~
:.. ~. , ;.
~ ing and/or precipitating effect on the calcium which is contained :''`'1 . ~:
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 ~ i :
as sequestering a~ents for calcium. However, these compounds s ; 3~ frequently have-the capacity of delaying the precipitation of `~' calcium carbonate from aqueous solutions." ' ',.:
'.

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, m~ 2-':~: ' . ' : ,: . .
, 5~1 D4~i ., ,.:
Preferably, amounts of seques-tering or precipitating agents of, for example, 0.05 to 2 gm/1, were added to accelerate or improve the re~oval of dirt. Preferred are amounts of 0.1 to 1 gm/l. Substantially larger amounts can also be used, but if phosphorus-containing sequestering or precipitating agents were ~, ~
usedJ their amount had to be so selected that the phosphorus -~
load of the sewage was ~uch less than with the presently used triphosphate-based detergents.
" ~ .
Copending, co~monly-assigned Canadian patent applica-tion Serial No. 198,560 ~iled April 30, 1974 discloses an ~ improvement in the above invention, consisting of the presence, ;i. in the aqueous liquor together with said aluminosilicates of from 1 part by weight of nonionic surface-active co~pounds and .;, ~ fro~ 0 to 3 parts by weight of anionic surface-active compounds, .,.,.,, ~
.-~ as said surface-active compound, sai.d nonionic surface-active .....
compounds being a mixture of a compound having a labile hydrogen ~t~1 and from 8 to 18 carbon atoms ethoxylated with from 8 to 20 ethylene oxide units and a compound having a labile hydrogen and from ~ to 18 carbon atoms ethoxylated with from 2 to 6 ethylene oxide units in a weight ratio of l:Q.2 to 2. An i~-proved soil removalJ particularly in the case of ~atty and oily :i'l soils, is achieved b~ the combination of the aluminosilicates . 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 soiled . , '~
;: textiles with an aqueous liquor containing compounds innibiting alkaline earth ~etal ion precipitation on said soiled textiles as well as optionally at least one surface-active co~pound 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 te~tiles substantially ' -3-.
~: ., .;
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:, , ~58~1D4~
.

soil~free, co~prising using a builder combination of (1) at . .
least one finely-dispersed9 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 activa sub~ ~ -'~. stance and the formula on the anhydrous basis .' (M2/nO )X Me203 (Si2 )y ~: where M is a cation of the valence n9 exchangeable with calciu~, ,.....
x is a number of from 0.7 to 1.5, Me is a member selected from th~ group consisting of alumin~m and boron, and y is a number : ............. . ...
~; 10 from 0.8 to 6, and (2) a combination of A) a water-soluble salt ~
exchangeable with cal~ium of nitrilotriacetic acid, B) an inor- -ganic phosphate capable of binding or sequestering calcium, and/or C) a wash alkali selected from the group consisting of : an alkali metal carbonate and an al~ali metal silicate, where ,. . ~
i the ratio by weight of component A) to components B) and/or C) ;~; is from 10:1 to 1:10, and the ratio by weight of component (1) to component (2) is 1:0.5 to 20; as said compounds inhibiting .~..................................................................... . .
alkaline earth metal ion precipitation ; A further object of the present invention is the development of a detergent system for washing soiled textiles .; .,. , .- .
comprising the above wate~-insoluble sillcate compound, the above water-soluble compounds including l~T~, and a textile ~r; detergent.

`-~ These and other objects of the invention will become more apparent as the description thereof proceeds.
~;, Thus, the present invention relates to an improved r.~
process for the washing and bleaching of textiles byr treatment of the same with an aqueous liquor containing substances able -' to sequester the compounds that make the water hard, where `'!:.'`" 30 finely divided, water-insoluble silicate compounds containing at -~; least some combined water and having a calci~ binding power o~
~, ;. . :

.. ;~ ,..
.: :., .,~.,~,................................................................. ..
, . ~. .
.; ' ..:
, ", .... ...
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at least 50 mg CaO/gm of anhydrous active subst~nce and the formula (I) on the anhydrous basis (M2/nO)X Me203 (Si2)~ (I) .~ where M is a cation of the valence n, exchangeable with calcium., . . . .
.. x is a number from 0.7 to 1.5, Me is aluminum or boron, and y ~
.,,. :
.-~ a number from 0.8 to 6, preferably from 1.3 to ~, are suspended .... .
. therein, as well as a further calcium-complexing or precipi- ~
.: .
i tating builder, and where the aqueous liquor also optionally .: contains a surfæce-active compound, characterized in that per ,. . .
;~: 10 part by weight of the compound of formula I, at least 0.5 parts by weight of a combination of ..
. A) nitrilotriacetic acid, in the for~ of a water~
~ ;, ~ soluble salt exchangeable with calcium, .;.:
~., B) an inorganic phosphate capable of binding cal-cium, and/or C) an alkali metal carbonate or silicate `,~ The combination of the components A, B and C used .:
according to the invention can also be present in amounts of 15 or 18 or more parts by weight per part by weight of the com-` 20 pound of formula I.
Due to the invention, a further improvement of the `s~ washing action is achieved, . .. : .
. The invention more particularly relates to a process . of treating soiled textiles by contacting soiled textiles with `~. an aqueous liquor containing compounds inhibiting al~aline .. ..
" earth metal ion precipitation on said soiled textiles as well : ,:
; as optionally at least one sur~ace~active compound for a time ... ~ sufficient to disperse or dissolve the soil from said soiled .. .. .
.:~ textiles into said aqueous liquor, separating said aqueous ,..~....
~ 30 liquor and recovering said textiles substantially soil-free~
: . .

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co~iprising using a builder combination of (1) at least one ~
` finely-dispersed) 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/nO)X . Me203 (SiO2)Y
~: where M is a cation of the valence n, exchangeable with calcium, ~.
.~ x is a n~mber of from 0.7 to 1.5, Me is a member selected from ~S.. ~ the group consisting of aluminum and boron, and y is a number ~ 10 from 0.~ to 6, and (2) a combination o~ A) a water-soluble j~. salt exchangeable with calcium of nitrilo-triacetic acid, B) ,: . , .
; an inorganic phosphate capable of binding or sequestering ;~ calcium, and/or C) a wash alkali selected fron the group con- ~
`~i sisting of an alkali metal carbonal;e and an alkali metal sili- :
` cate, where the ratio by weight of component A) to components ~` B) and/or C) is from 10:1 to 1:10, and the ratio by weight of compo~ent (1) to component (2) is 1:0~5 to 20, as said compounds ~
.s inhibiting alkaline earth metal ion precipitation. ~ -i~."
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The nitrilo-triacetic acid or its water-soluble salts exchangeable with calcium is designated hereafter as "NTA", the inorganic phosphates capable of binding calciwm is designated as "phosphates". The alkali metal silicates and carbonates are -~; also referred to undertheterm "wash-alkalis".
"
It is of advantage in the claimed method to use 0.45 parts by weight or more of NTA per part by weight of the compounds of formula I. The weight ratio of NTA to the other "~
co~ponents of the combination to be used according to -the inven-tion, that is, the weight ratio of component A to all the com-ponents from the group B and C is generally about 1:10 to 10:1.
..:.
` Weight ratios o~ about 1:5 to 5:1 are preferred.
The phosphates and the wash~alkalis can partly or completely replace each other within the ~ramework o~ the inven-tion. If the wash liquor is to have a very low phosphate con-~. :
tent, the amount o~ phosphates used generally does not exceed , ., 60~ by weight of the total weight of compounds of formula I, ., .
NTA3 and phosphates or wash-alkalis. Preferably the phosphate portion is 50~ or less of this total weight, With the use of the above described aluminosilicates according to the invention, it is readily possible to keep the phosphorus content of the ;
~ treatment liquors at not more than o.6 gm/l, pre~erably not more ,~ than 0.3 gm/l. ~owev0r, excellent results can also be achieved ~ with phosphorus-free compounds) if the wash~alkalis (component . ~, ~ C) are used instead of the phosphates (component B). -",.,;,, .
The alkali metal silicates are silicates in which `; the SiO2:Na20 ratio is between 0.66:1 and 4:1. Ratlos in the range between 2.3:1 and 3.45:1 are mostl~ preferred Depending on the desired alkalinity of the detergent and on the desired contribution which the silicate is to make to the alkalinity ~ of the detergent, higher or lower ratios may be fe~sible, for `~ example, in one case ratios in the range of between 1 and 2 3 _6_ , :

. . .

,..... ... '; . . ~,,: :~ . . ' . .. . ~ . . , . . :

~0~8~
...
,~ . .

;, .:: .
.: :. :'' s ' :
,.
can be employed (high alkalinity) and in another case ratios . , .
in the range between 2.3 and 3.45 can be employed.

;., In the complete absence o~ phosphates it is ~re~ -, . .
.
quently advisable to use about 5~ to 50~ by weight o~ a , .
Phos~honic acid, based on the total amount o~ component C~, -especially a polyphosphonic acid in the form of its water-soluble salt, capable of retarding the precipitation of dif~icultly soluble calcium compo~nds, or of any other organic ,. .
compounds with a calcium sequestering or calcium precipitation-retarding actionO
;~ The ~oint use of co~pounds of formula IJ NTA and `
phosphates or alkali metal carbonates or silicates has proven to be surprisingly advantageous. The cleansing efXect achieved ` `
~;i with the claimed method could be obtained heretofore only by ., : . .. ~
using much larger amounts o~ phosphate. The invention thus makes a contribution to the solution o* the so-called phosphate problem, that is, to the reduction o~ the excess of phosphates :, . i .
~ in the environment, which leads to eutrophication, particularly .,,.,~. ,: .
~X in stagnant waters.

The above-de~ined aluminosilicates can be produced ~ synthetically in a simple manner, ~or exa~ple, by reacting water .~,~, ,.

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~; solublo sll:Lcate~ Witll water-soluble aluminates in the presence of water. To ~hls en(l nqueous solutions of the starting materi-`, als can be mixed wlth each other, or one component wh:Lch ls . ~ present ln solid form can be reacted with another component ;'.~ . ' .
which is present as an aqueous solution. The desired aIumino-silicates can also be obtained by mixing both solid components : in the presence of water, preferably with comminution o the ....i -:
- mixture. Aluminosilicates can also be produced from Al(OH) 3, ~ Al203 or sio2 by reaction with alkali metal silicate or alkali `~ 10 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 transforming the melt into finely-dispersed products.
~ . . .
The cation-exchangillg aluminosilicates to be used accord-~ ing to the invention are only formed if special precipitation `'!~.'' conditions are maintained, otherwise products are formed which ~` have no, or an inadequate, calcium exchanging power. The calcium ,~ exchanging pow~r of àt least 50 mg CaO/gm of anhydrous active ~; 20 substance (AS) is critical to the present process. If alumino-~,~:;. . : .
silicates are employed with below the critical limit of calcium ;~' exchanging power, very little if any soil removal from the ;~;`` soiled textiles is effected.
; The aluminosilicates in aqueous suspension produced by ~ j precipitation or by transformation in finely-dispersed form according to other methods are obtained in an X-ray amorphous ~;` form. They can be trAnsformed from the amorphous into the aged ;~ ; or crystalline state by heating the suspension in water to tempera- .
tures of 50 to 200C. However, there is hardly any difference ~,` 30 between these two forms as far as the calcium binding power is .,;. "- ) `~ concerned. Aside from the drying conditions, the calcium blnding ~ power of the aluminosilicates is proportion~l to the amount of 5:;

~';;- mJpl f, ;r ~ ':
':' i~

s~
alumlnum conLn~n~d therein with reference to ~he amount oE

slllcon. Nevertheless, the crystalline aluminum sillcates are . .
preferred for the purpose of the invention. The preferred cal-i cium binding power, which i.5 in the range of lOO to 200 mg CaO/gm AS, is found primarily in compounds of the composition:
-; 0.7 to 1.1 Na2O . Al2O3 . 1.3 to 3.3 SiO2 This summation 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 Na2O . Al2O3 . 1.3 to 2.4 SiO2 : , b)- 0.7 to 1.1 Na2O . A1203 .>2.4 to 3.3 SiO2 .. ., . ..
~; The different crystal structures can be seen in the .. . . .
X-ray diffraction diagram. The d-values found are given in the ;~i examples in the description of the production of the alumino-... :.
silicates I and II.

`- The amorphous or crystalline aluminosilicate contained . ;, , - . .
` in the aqueous suspension can be separated by filtration from ,~ . . .
'~ the remaining aqueous solution and be dried at temperatures of ~;~ 50 to 400C, for example. Depending on the drying conditions, ,, 20 the product contains more or less combined water. Anhydrous products are obtained by drying at 800C. If it is desired to `;~ remove the water completely, this 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 for ~; the aluminosilicates to be used according to the invention, ., ;- preferably the temperature should 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 ls removed, can be used for the purposes of the invention. The aluminosilicates thus produced, which contain varying amounts of combined water, are obtained after ~' .,.
9~
; ~., , m~p/
. . .

:. : , , . ... ~ . ~ . , : . .. ;
.. , , .. , . , . : ... , ~ 5~0~L6 the dL~ln~e~ra-ion oL tlle dricd filter cake, as flne powders whose primary particle size does not exceed 0.1 mm, but is .....
mostly lower and ran~es down to dust fineness~ for example, to . , .
0.1 ~. It must be kept in mind that the primary particles can , ~ , , be agglomerated to larger structures. In some production ` methods primary particle sizes ranging from 30 to 1 ~ are :, .
` obtained.

Of particular advantage are aluminosilicates having :,:
at least ~% by weight of particles of 10 to 0.01 ~, preferably 8 ; 10 to 0.1 ~. These aluminosilicates preferably contain no primary ~,; or sécondary particles above 30 ~. As far as the products are ; .. , :.
~` crystalline, they are "micro-crystalline".
The formation of smaller particle siæes can already be enhanced by the precipitation conditions. For these smaller particle sizes, the intermixed aluminate and silicate solutions, which can also be introdnced simultaneously into the reaction vessel, are subjected to great shearing forces. If crystalline `;l aluminum silicates are produced, which are preferred according i ~
`` to the inventi.on, 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 advisab]e to ~, remove these secondary particles in a suitable manner, for exam-ple, by air sifting. Aluminosilicates obtained in coarser Eorm, '" . "' ' !
~; which are ground to the desired particle size, can also be used.

~i~ Suitable for this purpose are, for example, mills and/or air ,: ,. .
sifters or combinations thereof. The lattie-r are described, for ;` example, in Ullmann, "En~yklopadie der technischen Chemle" Vol. 1, 1951, p. 632 to 634. ~ ;

A considerable improvement in the products, i.e. the ~i5 washing result with the compounds used according to the invelltion '.!'``.``" iS achieved by the use of aluminosilicates with lo~er calcium-~-~ m~p/
' t,~ , ,; ,' `

~L13S~C~4~:
bindln~ capaci~y.
It is also advantageous for the purposes according to the invention to utillze products that are still moist lmmedi-ately after their precipitation or even in suspension (without intermediate drying), such as i.:
~ 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 aluminosilicate from which the mother liquor ~;; 10 was partially removed, ; , c) a still flowing suspension of a]uminosilicate in waterS obtained after partial or complete rinsing out of the `v mother liquo-r, or `~; d) an aluminosilicate from which the rinse water was partially removed.

What has been said about the primary particles applies ''i"i' ~ ' to aluminosilicates that are still moist, in suspension or in ;
t-~ the form of a slurry.
From the sodium aluminosilicates, aluminosilicates of other cations, for example, those of potassium, magnesium or water-soluble organic bases can be produced in a simple manner ~;, j .
~; by the exchange of bases. The use of these compounds instead of the sodium aluminosilicates may be of advantage if a special ~;
~` effect is to be achieved by the supply of the said cations, for i ~` ' ':.
example, if the state of dissolution of different surface-active compounds simuItaneously present in the composition is to be influenced.
These prepared aluminosilicates, that is, produced prior to their use, are used for the purposes of invention.

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' ~S~ 6 The amount of the combination o~ the compounds according to ~ormula I with the combination o~ NTA with phos-phate and/or ~ash-alkalis required to obtain a good washing and cleansing e~fect according to the invention depends, on the one hand, on the calcium binding power of the al~minosilicate, and on the other hand, on the amount and degree o~ soiling o~ the textiles to be treated and on the hardness and the amount of water used. If the washing is conduct~ with a hard water, it is advisable to select the amount of the combination o~ the compound of ~ornula I/NTA/phosphate or wash-alkalis so that the residual hardness of the water does not exceed 5 dH (German hardness, corresponding to 50 mg CaO/l), pre~erably 0 5~ to

2 dH (5 to 20 mg CaO/l). In order to obtain an optimum washing e~fect, it is advisable, particularly with greatly sollcd tex-tile~, to use a certain excess o~ the total combination, in order to bind completely or partially the hardness constituents contained in the released soil. Fa~orable concentrations o~
the aluminosilicate/NTA/phosphate or wash-alkalis combination ,...;
can thus be in the range o~ 0.2 to 10 gm/l, pre~erably 1 to 6 gm/l~ where the amount of the alumiinosilicate is calculated ~ on an anhydrou~ (AS) basis.

,~ The inorganic phosphate binding calcium is preferably :',: ... .
~.~ a water-soluble tripolyphosphate, particularly an alkali metal ;r. . ''. :tripolyphosphate, like the highly suitable pentasodium tripoly-.'~ phosphate. However,other alkali metal condensed phosphates ii, such as the pyrophosphates and hexametaphosphates9 may be i;. employed.

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The process accord:lng to the inventlon operatlng w:lth ; the use oE synthetlc, preferahly crystalline alumlnosillcates, ~ is suitable 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 textiles which contain high- -ly processed cotton or synthetic ehemical fibers, like polyamide, ~ 10 polyester, polyacrylonitrile, polyurethane, polyvinyl chloride ,; or polyvinylidene chloride fibers. The detergents according to the invention can also be used for washing synthetic fiber-cotton blends called "wash and wear", occasionally also "no-iron"
~` fabrics.
When washing by using cleaning liquors eontaining aluminosilicates in aqueous suspension9 the washing or cleaning ~ ean be improved by common ingredients of these wash liquors.
.~;. .
These include, Eor example, surface-active compounds, surface-aetlve or non-surfaee-aetive foam stabilizers or inhibitors, textile softeners, chemieal bleaches, as well as stabilizers and/or activators for the latter, soil suspension agents, eorrosion-inhibitors, anti-microbial substances, enzy~esj -brighteners, dyes and perfumes.
When using one or several of the above-mentioned sub-stances, normally contained in wash liquors, the following con-~ eentrations are preferably maintained:
?~f~ 0 to 2.5 gm/l of surface-activP compounds 0 to 0.4 gmtl of activated oxygen or equivalent amounts of aetivated ehlorine as a bleach.

The terms "aetivated oxygen" and "actlvated chlorine"
axe employed as meaning bleaching compounds wi~h an ... .
~ i..................................................................... .
~ -13-, . . .
; m~
,... ..

`:

oxygen-oxygen bond or a chlorine content, with the given amounts referring to the active oxygen or chlorine, respectively, The pH-value of the liquors can be between 6 and 13, preferably between 8,5 and 12, depending on the type Qf textile j to be washed.
; The invention furthermore relates~to preparations for carrying out the method according to the invention. These contain the finely-divided, water-insoluble silicate compounds ; ,"- ~ .
~` of the above indicated formula I, which have in the aqueous treatment liquor a calcium binding power of at least 50 mg : .
CaO/gm o~ anhydrous active substance. Optionally, they also ~` contain the special sur~ace-active component descrlbed above.
;; The preparations according to the invention are characterized in that the~ contain, as a further development, at least 0.5 parts by weight of a combination o~
A) Nitrilotriacetic acid in the form o~ a water-soluble salt exchangeable wi-th calcium, i;i~ B) a calcium binding phosphate and/or ~i ~ C) an alkali metal carbonate or alkali metal ?~
silicate ~'~ per part by weight of the co~pound of ~ormula I.
More particularly~ the present invention also relates ~ to a co~position for use in washing agent compositions consist-:t;~ ing essentially of (l) at least one finely-divided, water-.~, ;.
insoluble silicate co~pound containing at least so~e combined water and having a calcium binding power of at least 50 mg Cao/g~
~` of anhydrous active substance and the formula on the anhydrous -; basis -.
(M2/n)X ~ Me203 (si2)y 30 where M is a cation o~ the valenca n, exchangeable with calcium, ;
x is a number of from 0.7 to 1.5, Me is a member selected ~rom ; . .

'~. ~'' , .

', :. . . ' . : , ' ' ~' ~ . ' ~ the group consisting of alumin~ and boron, and y is a nu~ber ~ . .
from 0.8 to 6, (2) a combination of A) a water-soluble salt exchangeable with calciu.m of nitrilo-triacetic acid~ B~ an inor-ganic phosphate capable of binding or sequestering calciu~, and/or C) a wash alkali selected froim the group consisting of an alkali metal carbonate and an alkali metal silicate, where the ratio by weight of component A) to components B) and/or C) is from 10:1 to 1:10, and (3) at least one surface-active com-,, .
pound selected from the group consisting of anionic surface- ;
; 10 active compounds, nonionic surface-active compounds and ampho-teric surface-active compounds, where the ratio by weight of component (1) to component (2) to component (3) is 1:0.5 to 20:0 to 5.
~ .
By introducing the preparations according to the invention into water, wash liquors for textiles to be used ., i~;
according to the invention are obtained.

.~ The data concerning the ~uantitative ratios and ~ "., the quality of -the compounds contained in the treatment liquors ' apply correspondingly also to preparations according to the ,. . . .
;~ 20 invention.
Thus the amount of the polyphosphates contained in the preparations according to the invention is preferably not greater than that corresponding to a total phosphorus content -of the preparation of 6~, preferably 3~. The percentages are by weight . 1:'.'' .
"~ Accordingly, the total weight of the compounds be-~ longing to the groups A, B and C should be up to 15 or 18 to `` 20 times higher than the amounts of the compounds of formula I.

Particularly good detergents can be found in the range in which the total amount of the compounds of the groups A, B and C is . ; .
about 0.5 to 3 parts by weight per part by weight o~ the com-pounds of formula I, but also the range in which about 3 to 18, ".. ~ ' , ..

:','.................................................................... ..

-. :. . . ~

:, ~

: -.

`:.

particularly about 9 to 15 parts by weight of the compounds A, B or C are present per part by weight of the compound of formula i:;, I is satisfactory.
The preparations contain preferably at least one ~; surfactant. The composition of typical textile detergents to .. .
~ be used at te~peratures of 50 to 100C is wi-thin the following .:
~ ~ormulation:
:..
; from 5~ to 40~, particularly 5~ to 30~ anionic and/or - nonionic and/o~ amphoteric surface active compounds, ;; 10 from 10% to 95~ of the builder combination according ~ to the invention consisting of NTA and phosphate and/or wash ; ~............ . ...
alkalis, and including the silicates of ~ormula I, ; ~ro~ O to 50~ of bleaching agents, as well as other :;
,, "I r,~ , : .
; additives ~ostly found in small amounts in textile washing agent ~i compositions. ~ -. In particular the complete composition of the present invention is a washing agent composLtion consisting essentially ~ ~ . .. ..
~; of (I) from 5~ to 40~ by weight of at least one æur-face active compound selec-ted from the group consisting o~
,........................................................................ . .
. anionic surface-active compounds, nonionic surface-active co~
'~`'$~'. pounds and amphoteric surface-active compounds, ~ (II) from 10~ to 95% by weight of a builder component .... .
1 consisting essentially of (1) at least one finely-divided, water-., . ~ , insoluble silicate compound containing at least so~e co~bined ~;i,? water and having a calcium binding power of at least 50 mg CaO/gm of anhydrous active substance and the for~ula on the ;;~ anhydrous basis ~-'~,!, (M2/n~X ~ Me23 (si2)y `' ~ 30 where M is a cation of the valence n, exchangeable with calcium~ --. . . ~
~,' '' ,.
.,.:,., : . -;, . .
~;'''..
~'" '~ ,'' ,~" ,;

~0~8134 6i r ,~ ~
,.
, . .
,-~; x is a number of from 0.7 to 1,5, Me is a member selected fro~
` the group consisting of aluminum and boron, and y is a number from 0.8 to ~, and (2) a combination of A) a water-soluble salt exchangeable with calcium of nitrilotriacetic acid, B) an inorganic phosphate capable of binding or sequestering calcium, ~ and/or C) a wash alkali selected fro.n the group consisting of `;i an alkali metal carbonate and an alkali metal silicate, where the ratio by weight of component A) to components B) and/or C) ... . .
~li is from 10:1 to 1:10, and the ratio by weight of co~ponent (1~ i ,.,; .
to component (2) is 1:0.5 to 20, and (III) from 0 to 50~ by weight of at least one of the following: foam stabilizers or inhibitors, chemicalbleaches as well as stabilizers and activators therefore, soil suspension agents, corrosion inhibitors, antimicrobial compounds, enzymes, optical brighteners, dyes, and perfumes~
~ Preferably the tenside co~binations in which low and `~ high ethoxylated compo~ds are present, optionally, in combina-tion with anionic tensides are employed as surface-active com-pounds, The nonionic surface-active compounds or tensides (nonionics) to be used are addition products of 2 to 6 or a to 18 mols of ethylene oxide onto 1 mol of a fatty alcohol, an alkylphenol, a fatty acid, a fatty amine, a fatty acid amide ; or an alkane sulfonamide. The fatty, alkyl or alkane portion '`j!'~'``~ of the molecule has from 8 to 22 carbon atoms. Particularly ; , important are the stric-tly aliphatic nonionics derived, for example, from coconut or tallow fatty alcohols~ from oleyl alcohol or fro~ secondary alkanolsJ all with 8 to 18, preferably ,. .................................................................... .
: .
..,.::
;~ =17-,. ` .
, ,.................................................................... ~
. ., . ,~ . .
.... ...
; `.
. . .
.;

i: -

3~ 580~6 `:
, . . . ~ , ;j ; . ` .

.... . .
~ 12 to 18 carbon atoms.
. ,~ .
!`'',~" Also useable as nonionics are the additian products .-of ethylene oxide and ter~inal or non-ter~inal vicinal alkane~
;;l diols having from 8 to 20 carbon atoms, preferably those with ~ :
~`, 2 tol4 and 8 to 12 ethylene glycol units, respectively, in the .;,' molecule. ~ ~
~; . Also present in the detergents according to the in- . --. :
~, vention may be organic sulfonic acids, carboxylic acids and :~
. sulfocarboxylic acids that are not surface-acti~e and contain .. :
~` 10 1 to 8 carbon atoms, These areJ for example, water-soluble ~-.
. salts of benzene sulfonic acid, toluene sulfonic acid or xylene sul~onic acid~ water-soluble salts of sul~oacetic acid~ sulfo-benzoic acid or of sul~odicarboxylic: acids~ :
The amount o~ the aluminosilicate compounds of ~ :
for~ula I in the washin~ agent compositions according to the invention is usually about 5~ to 40~ by weight. Lower amounts . o~ 1, 2, 3 or 4~ can also be of advantage, however, as well as higher amounts occasionally. ..
With regard to the other tensides, ~oam inhibitors, :.
foam stabili7.ers~ bleaching agents and stabilizers and/or activators for the latter, soil suspension agents~ enzymes and optical brighteners to be used in the preparations and in the .... ~ : .

;-1'`. '.' ' -''''" '.

~v -18~

"

;` -`"
''i` f~S~
`
/:

J,.'.
; ':
method according to the invention~ these are discussed in detail later. The data given there, also regardin~ the alu~ino-silicates to be used, apply here correspondingly.
Of particular practical interest are thepreparations of powdery to granular consistency, which can be produced ac- -cording to any method known in the art. In order to facilitate the production and handling o~ the products, it ~ay be advisable to use the alu~inosilicate co~pounds of for~ula L in the for~
of agglomerates. It is generally preferred if these agglom-erates break down in use, ~or exa~ple, with re-for~ation o~ the primary particles.
For the production, the powdery colmpounds o~ ~ormula I can be mi~ed in a si~ple ~anner w:Lth the other components of the detergent; the oily or pasty compounds, such as nonionics, can be sprayed on the powder. Another possibility consists in incorporating the powdery aluminosilicates in the other com-:, .ponents o~ the preparations, which are present as an aqueous sludge, which is then transformed into a powder by crystalliza-tion or by drying the water with heat. The possi~ility o~ ~ix-ing components of the preparation with the components of ~ormula I which are still wet from the production, has already been mentioned. Heat-and moisture-sensitive components can be incor-porated after hot~drying, either on belts or in spray dry~ng ; .. -, ., towers These include the bleaching components 9 activators for the latter, enzymes, antimicrobial substances etc. `~
., .:,. .

~, -19- `:
.. "., ~
",...
.. . ~
:~.," ' , ~: ., ,~, ..
. . , i... ,:, ' , : ' , ': ' .
: ,,, , . ~ . .

l~S~30~
The surface-ac~lve compoun(Is or tensides contaln ln the molecu:le at least one hydropIIobic or~anic moiety and one water-solubili~ing, anionic, non ionlc or amplIoteric ~roup.
The hydrophobic moiety is mostly an aliphatic hydrocarbon radlcal with 8 to 26, preferably 10 to 22 and particularly~l2 to 18 carbon atoms or an alkyl aromatic radical, such as alky]phenyl, with 6 to 18, preferably 8 to 16 aliphatic carbon . , , :
atoms.

Among 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 o the sulfonates, sulfates and synthetic carboxylates.

Suitable anionic tensides of the sulfonate type are alkylbenzene sulfonates (C~_I 5 alkyl) mixtures of alkene-~...................................................................... .
sulfonates and hydroxyalkanesulfonates, as well as alkane-~; disulfonates, as they are obtained, for example, from m-onoolefins -` with terminal or non-terminal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hy-drolysis of the sulfonation products. Also suitable are alkane-`` sulfona~es which are obtained from alkanes by sulfochlorination i.,.;.................................................................. . .
.~ or sulfoxidation and subsequent hydrolysis or neutrali~ation ~,., or by ~isulfite addltion to olefins. Other suitable tensides of the sulfonate typè are the esters of a-sulfofatty acids, for 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 al-~ cohols, tallow fatty alcohols or oleyl alcohol) and those of sec-?~.
ondary alcohols. Also suitable are sulfated fatty acid alkanola-- ~ mides, sulfated fatty acid monoglycerides or sulfated reaction products of 1 to 4 mols of ethylene oxide with primary or ,5,..
o '.' ' i: mJp/
,. . . . .

: - .~ : . . . . :.

~ `
}i;

!,', necondllry fat~y nlcohols or alkylphenols.
Other su:Ltable an:Lonlc tensides are the f'atty acid e6ters or amides of hydroxy- or amino-carboxylic acids or sul-fonic acids, such as the fatty acid sarcosides, fatty acid , glycolates, fatty acid lactates, fatty acid taurides or Eat-ty ,~ acid isoethionates.
.;,~;~. .
The anionic tensides can be present in the form of their alkali metal salts, such as the sodium or potassium `~'`' salts, the ammonium salts, as well as soluble salts of organic bases, such as the lower alkylolamines, for example, mono-, di- or triethanol amine.
~` Suitable non-ionic surface-active compounds or ten-~,t~ . .
sides are the addition products of 4 to 40, preferably 4 to 20 mols of ethylene oxide to 1 mol of a fatty alcohol, alkyl-phenol, fatty acid, fatty amine, fatty acid amide or alkane-` sulfonamide. Particularly important are the additional products of 5 to 16 mols of ethylene oxide to coconut fatty alcohols or tallow fatty alcohols, to oleyl alcohol or to secondary alkanols with 8 ~o 18, preferably 12 to 18 carbon atoms, as well as mono-alkylphenols or dialkylphenols with 6 to 14 carbon atoms in the alkyls. In addition to these water-soluble non-ionics, polyglycol ethers with 1 to 4 ethylene glycol ether radicals in the molecule, which are insoluble or not completely water-soluble, are also of inte~est, particularly if they are used together with water-soluble non-ionic or anionic tensides.
Furthermore, ehe 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 alkylenediamine-polyoxypropylene glycol (Tetronics ~ ), and to alkylpolyoxypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, can also be used where tha '; polyoxypropylene glycol chain acts as a hydropllobic radical.
, ~, :
. .
.; ~ -21- `
p/
.'::. . ' ~;
~:",,, . , ~
. . . .
,,, . - . , . . .

~8~6 .,''~ :
Non--:Lonlc ten~ides of the type oE the nmlne oxides or ~ulfoxidcs can also be used, ;-The foamlng power of the tenside can be Lncreased - or reduced by combination of sultable tenside types. A re-duction can also be achleved by additions of non-surface-; active organic substances.
Suitable foam stabili~ers, 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, fatty alcohols or higher .j, .
`~ terminal diols have been suggested for this purpose. ~.
A reduced foaming power, that is desirable for the ;~
use in washing machinss, is often attained by combination of ~ -- different tenside types, such as of sulfates andlor 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 satur-`~ ated C2 0-24 fatty acids have been provèn good as foam inhibi-. .~ . , .
tors. ~ ;
, , The non-tenside foam inhibitors included N-alkylated aminotriazines, optionally containing chlorine, which are obtained by the reaction of 1 mol of cyanuric acid chlorid2 with 2 to 3 mols of a mono- and/or dialkylamine with 6 to 20, ;
preferably 8 to 18 carbon atoms in the alkyl radicals.
Similarly effective are propoxylated and/or butoxylated amino-triaæines, 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 this propylene-oxlde derivative.
., . ,.. - .
Likewise suitable as non-tenside foam inhibitors - are water-insoluble organic compounds, like paraffins, or ~ ..................................................................... . .
~ halo~enated paraffins with melting points below IOQ~C, ali- , .... .
.. ' ;~:
. .,. ' , -, m~p/ -22-~:.~. :.- .
,, . ;~ .

phatic Clu to C.,0 kctones, as well as nliphatic carboxyllc acld e~ter~ wllich con~ain ln the acld or alcohol resldue, ~- optionally, also ln both of these residues, at least 18 .'i' carbon atoms (such as triglycerides or fatty acld/fatty alcohol esters). These compounds can be used to reduce foamlng, particularly in comblnations of tensides of the sulfate and/or sulfonate type with soaps.
~articularly low-foaming non-ionlcs, which can be used either alone or in combination with anionic, amphoterlc and non-ionlc tensides, and which reduce the foaming power of high-foamlng tensides, are the addition ~ , .~, . . , - .
products of propylene oxide on the above-described surface-;~ active polyoxyethylene-glycul ethers as well as the likewise- -, .
~i described addition products of ethylene oxide to polyoxy- `
-~ propylene glycols and to alkylenedianline polyoxypropylene ,. . ~ :
~" ~
glycols or to alkyl polyoxypropylene glycols having 1 to 10 carbons in the alkyl.
-~ Among the compounds serving as bleaching agents ~`, and releasing HzC2 in water, sodium perborate tetrahydrate (NaB02. H203. 3 H20) and the monohydrate (NaB02. H~02) are - `
of particular importance. But also other H202 releasing borates can also be used, such as perborax Na2B40, . 4 H20.
These compounds can be replaced partly or completèly by other carriers of active oxygen, particularly by peroxyhydrates, ~ such as peroxycarbonates, (Na2C03 . 1.5 H202), peroxypyro-i`, phosphates, citrate perhydrates, urea-H202 compounds, as ~`~
~ell as by H202-releasing peracid salts, such as Caroates - ~.
` (KHS0~), perbenzoates or peroxyphthalates.
~ It is recommended to incDrporate water-soluble ;` 30 and/or water-insoluble stabilizers for the peroxy compounds ,~ together with the latter in amounts of 0.25% to 10% by weight. Water-insolub:Le stabilize~s, which amount to 1% to ~-~:'', '-, . , , . . .
. m~p/ -23 " ', . '~
~ ": ~ , ":, : ,: , . . .
.

3C34~
.. . .
~%, prerer.ll)ly 2~ to 7% o the wel~ht of the entlre prepar-atlon arc, for example, the magnesium havlnp a MgO : SiO2 ratio of 4:1 to 1:4, preferably 2:1 to 1:23 and particularly 1:1, which are mostly obtalned by precipitation from aqueous solutions. In thelr place, other alkallne earth metal, cadmium or tin silicates of corresponding compositions are also usable. Also hydrous oxides of tin are suitable as stabilizers. Water soluble stabilizers, which can be present ~;~ together ~7ith water-insoluble stabilizers, are mostly the ` 10 organic sequestering agents which can be added in amounts of ~i~ 0.25% to 5%, preferably 0.5% to 2.5% of the weight of the entire preparation.
, " . .
In order to obtain a satisfactory bleaching ~; effect then washing at temperatures belo~ 80C, particularly ~; in the range of 60 to 40C, activator-containin~ bleaching components are preferably incorporated in the preparations.

~Si~; Certain N-acyl and/or O-acyl compounds forming, ::' . -with H202, organic per acids serve as activators for per i~ compounds releasing H202 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'-tetra-acylated amines, such as N,N,N'9N'-tetraacetyl-methylene-~;` diamine, N,N,N',N'-tetraacetyl-ethylenediamlne, 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-~` mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxy-:;.. .~', . . .
'.`;.~ benzamide, the N-acylated cyclic hydrazides, acylated ~i '~ 30 triazoles or urazoles, such as monoacetyl maleic acid hydra-~ zide, the 09N,N-trisubstituted hydroxylamines9 such a`s ~ ~ .
; O-benzoyl~N,N-succinyl-hydroxylamine, O-acetyl- N,N-succinyl- ~
... .
":..:.
, . . .
,:~
' ~ ! ' ;~ mJp/ -24-; ,:, ",.,

4~16 hy(lroxylall~Jlle, O-p-mel:hoxybcnzoyl-N ,N-succinyl-hyclroxyl-amine, 0-p-nitrobenzoyl-N,N-sllccinyl-llydroxylallline and 0,N,N-triacetyl-hydroxy]amine, the N,N~-diacyl-sulfuryl-aTnides, such as N,N'-dimetllyl-N,N'-diacetyl-sulfurylamide, and N,N'-diethyl-N,N'-diethyl-N,N'-dipropionyl-sulfuryl amide, the triacyl cyanurates, such as triacetyl cyanurate ' or tribenzoyl cyanurate, the carboxylic acid anhydrides9 ,,"., .' such as benzoic acid anhydride, m-chlorobenzoic acid . anhydride, phthalic acid anhydride, 4-chlorophthalic acid ; 10 anhydride, the sugar esters, such as glucose pentaacetate, ;` the,1,3-diacyl-4,5-diacyloxyimidazolidines, for example . the compounds 1,3-diformyl-4,5-diacetoxy-imidazolidine, j; 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-., 4,5-dipropionyloxy-imidazolidine, the acylated glycolurils, such as tetrapropionyl glycoluril or diacetyl-dibenzoyl ;~,, , , ' 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-~'i piperazine, the acetylated or benzolylated products of ~,` 20 propylene-diurea or 2,2-dimethyl-propylene diurea [2,4,6,8-tetraazabicyclo-(3,3,1)-nonane-3,7-dione or its , . . .
~ ` 9,9 dimethy~ derivative], and the sodium salts of i,; p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxycarbonyloxy)~
.; . . - ~.
benzene sulfonic acid.
The activated chlorine compounds serving as . bleaching agents can be of an inorganic or organic 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 .,,, :
t'`,'', alkali metai pyrophosphates and polyphosphates, or with ,.. : ., . :~
~ alkali metal silicates. If the washing agents and washing : .;, ::
.:: :,~ .

,~ m~Pt -25-: ,`. .................................................................... .
,, ", : .
,' . ' ' ', ; ~ i , . . .

1058046i asslstant composltions contain mono-persu]rates and .. . . .
chlorides, active chlorlne is formed in aqueous solutlon.
., .
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 nitrogen atoms leading preferably to : a negative group, particularly to a C0- or S02-group.
:-...................... ...
These compounds include dichlorocyanuric acid and trichloro-. ,.'~ j ' cyanuric acid or their salts, chlorinated alkylguanides or ...... .
alkylbiguanides, chlorinated hydantoins and chlorinated . . .
melamines. -:,.:.................... , :
~; The preparations according to the invention can '~1 furthermore contain soil suspension agents Ol dirt carriers, which keep the dirt released from the fibers in suspension : . .:, ~, .:
in the liquor and so prevent graying. Suitable compounds ~ -are water~soluble colloids, mostly of an organic nature, 1 such as the water-soluble salts of po].ymeric carboxylic :,.... .
acids, glue, gelatin, salts of ether carboxylic acids or !`
ether sulfo-nic acids of starch or cellulose, or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable ~: for this purpose. Furthermore, soluble starch preparations ~;
and other than the above-mentioned starch products can be ~;.: ~ .. - :, used, for example, degraded starches, aldehyde starches etc.
~ Polyvinyl pyrrolidone can also be used.
ii The enæyme preparations to be used are mostly a , mixture of enzymes with different effects, such as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, ~- peroxidases, ureases, isomerases, lyases, transferases, ;~
.- 30 desmolases, or nucleases. Of particular interest are the .; ;.................................................................... .i.:
j~-'; enzyn)es, obtained from bacteria strains or from ~ungi, such ~;.~',.,. ;~.
~ ` as Bacillus subtilis or Streptomyces grlseus, particularly 1.`': ~. . '. ' ' .
,:.;,, :
, ~ " ;.
mJ~I -26-,"., :
. .,.,~, .

~L~5~ 6 ' ' pro~ea~es alld amyl.lses, whlch are relatively stable towards i; allcali6, percompounds, and anionic tensides and are still ''' effective at temperatures up to 70C.
'- Eni-~yme preparations are marketed by the manu-"' facturers mostly as aqueous solutiolls of the active substances .., or as powders, granulates or ~s cold-sprayed products. They '~ frequently contain sodlum sulfate, sodium chloride, alkali :: .
`~ metal ortho-, pyro- and polyphosphates, particularly tri-.~:
polyphosphate, as fillers. Dust-free preparations are ; 10 particularly valued. These are obtained in a known manner '~" by incorporation of oily or pasty Nonionics or by granulation' with the aid of melts of water-of-crystalli~ation-containing salts in their own water-of-crystallization.
.. - . .
Enzymes may be incorporated which are specific ~' for certain types of soil, for example, proteases or amylases ,; ' .~
'''~ or lipases. Preferably, combinations of enzymes with different . .
effects are used, particularly combinations of proteases and ~'` amylases.
The washing agents can contain optical brighteners`
~` 20 such as those for cotton, particularly derivatives 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 '`' similarly compounds which have lnstead of the morpholino ~ group, a diethanolamino g~oup, a methylamino group or a :.. .
~ 2-methoxyethylamino group. Brigh~eners for polyamide fibers ~
s ~:
- which can be used are those of the type of the 1,3-diaryl-2-;,.,i - :
pyrazolines, for example, the compound l-(p-sulfamoylphenyl)-3-(p-chlorophenyl)-2-pyra~oline, as well as compounds of ~ 3Q similar composition which ha~e instead of the sulfamoyl ''i;; group, for example, the methoxycarbonyl group, the ~'~ 2-methoxyethoxycarbonyl group, the acetylamino group or the ~ ' ' '', .
, ., ~
, .,~,, , ~ m~p/ -27-, ~, . .
:; :

., : :

vlnylsu].fonyl ~roup. Suitablc polyamide brighteners are a].80 the sub~stituted uminocumarills, for example, 4-methyl-7-dimethylamino-cumarln or 4 methyl-7-diethylaminocumarin.
Furthermore, the compounds 1-(2-benzimidazolyl)-2-(l-hydroxyetllyl-2-benzimidazolyl)-ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can also be used as polyamide brighteners. Brighteners for polyester and polyamide fibers which can be used are the compounds 2,5-di-(2 benzoxazolyl)-~r,;
thiophene,2-(benzoxazolyl)-naphtho-[2,3-b]-thiophene and 1,2-di-(5-methyl-2-benzoxazolyl)-ethylene. Furthermore, brighteners ~ ~ .
: of the type of the substituted 4,4'-distyryl-diphenyls can be ,~:~,~ . I .
utilized, for example, the compound 4,4'-bis-~4-chloro-3-sulfostyryl)-diphenyl. Mixtures of the above-mentioned .',.',.': ., .
;~ brighteners can likewise be used.
, The following specific embodiments are illustrative of the invention without being limitative in any respect.

E X A M P L E S
.'~.';': ~ -~l First, the production o the finished alumino- ~
~.. ; , .
' silicates is described, for which no invention is claimed.

Other aluminosilicates useful in the invention are described in the first filed S.N. 197,628 referred to hereinbefore.

' . PROCESS CONDITIONS

-~ The aluminate solution, diluted with deioni~d ~ .' water was mixed in a vessel of 15 liter capacity, under vigorous .~j,, , . ~. .
stirring with the silicate solution. Both solutions were at room temperature. An X-ray amorphous sodium aluminosilicate ~
~; was formed in the exothermic reaction as a primary precipitation ;
product. After stirring for 10 minutes, the suspension of the 't,,~" precipitation product was either separated as an amorphous 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 ~'. ' " .
, ', , .'' , :
m~ p /

. ~ ~ .
~ . I i . . . . . . .

. ~5~46 .' ,~. -~ .
and waullLn~ with delon:L~ed water unt-ll the outflowing wash water had n p~l-value of about 10, the fllter residue was dried.
. ~ :
When there ls any deviatlon Erom thls general production ,~, .
procedure, this is mentioned explicitly in the specific part.
Thus, for example, in some cases for the practical tests, the homo~enized uncrystallized suspension of the precipitation product or the crystal sludge was used. The water content was determined by heating the product for one hour to 800C.
~'~'. ' In the production of microcrystalline alumino-silicates~ indicated by the suffix "m'~, the aluminate solution ; ~ diluted with deionized water was mixed with the silicate solution `~
and mixed in a high.speed intensive stirrer (10,000 rpm, "Ultraturrax"~, made by Janke & Kunkel IKA-Werk, Stauffen/
; Breisgan/Federal Republic of Germany). After vigorous stirring for 10 minutes, the suspension of the amoi-phous precipitation i` 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 pH value 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 distribution was deter-mined 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 nluminosilicates or "~

. " ` . . , ~ ~.
m~ 2~
~ i :"
:~' , ~ .:
!. ~ "

;. ` . :
~5~

borosi.llca~c~ was det~rmlned l.n the following manner. 1 liter :'. of an aqueotls ~olution, containlng 0.594~gm of CaCl2 (~ 300 mg CaO/l ~ 30dll) and ad~usted to a pH of 10 with diluted NaOH, was mlxed 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 (+ 2~C).
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/gml As according to the formula:
: . 10. (30 x) . 10 .-~` ~ If calcium binding power is determined at higher temperature, for example, at 60C, better values are obtained .~ than at 22C. This fact distinguishes the aluminosilicates , j, . ~ .
from most of the soluble sequestering agents that have been ~-:` suggcsted so far for use in detergents and represents a particu- .
.,~ . .
~: lar technical progress in their use. ;
,:. . i.
~ Production conditions~for aluminosilicate I: ;;.
., ,i ;: . ~
Precipitation: 2.985 kg of an aluminate solution of ~.he '.` composition: 17.7% Na20, 15.8% Al203, 66.6% H20 iij~; 20 0.15 kg of sodium hydroxide . 9.420 kg o~ water ,~
2.445 kg of a 25.8% sodium silicate solution of the composition 1 ~a20. 6.0 SiO2, pxepared freshly from commercial waterglass and easily alkali-soluble silica Crystallization: 24 hours at 80C

Drying: 24 hours at 100C
~ .;
.. ~ Composltion: 0.9 Na20 . 1 Al209 . 2.05 SiO2 . 4.3 H20 (= 21.fi% H20) Degree of crystal-lization: Fully crystalline Calcium binding power: 150 mg CaO/gm AS.
?~. . .
~ mJp~ . ~30- . ;.
,1,~ , . -, .1 : . , ' , .

5~6 ;, `
I l:he product: obtnined was dried for 1 hour at 400C~ an alumin-lm silical:e Ia was obtained o:E the composition:
~', 0,9 Na20 . 1 Al209 . 2.04 SiO2. 2.0 Il20 (~ 11.47G 1120) " whlch is likewlse suitable Ior the purposes of the invention.
., - .
Product conditions for_luminosi]icate II:
Precipitation: 2.115 kg of an aluminate solution of the ' ::
composition: 17.7% Na20 15.8~ Al203, 66.5% H20 . 0.585 kg o sodium hydroxide .,, ~
io 9 . 61S kg of water ,; :
2.685 kg of a 25.8% sodium silicate solution ; of the composition: 1 Na20. 6 SiO2 (p re-,.. :. ~:
'~ pared as under I) .
Crystalliæation: 24 hours at 80C
Drying:24 hours at 100C and 20 torr.
`', Composition:0.8 Na20. 1 Al203. 2.655 SiO2. 5.2 H20 i::;.. :.` ` :
, ~ Degree of crystai-~, lization:Fully crystalline i;'.`: ' `;'~" Calcium binding `
`~' 20 power:120 mg CaO!gm AS. ~ ' .~... , . ~
`: This product too can be dehydrated by dr~ing (for 1 hour at 400C) to the composition:
:..... ;.~ :
! 0.8 Na20. 1 Al203. 2.65 SiO2. 0.2 H20 ~- This dehydration product IIa is likewise suitable for the purpose of the invention. `
The aluminosilicates I and II show in the x-Tay ~-,;,;~ .
.` diffraction diagram the following interference lines.
j d~ values, recorded with Cu-Ka- radiation in A ~, `j~ I II
- 14.
,,;., " ., 12.4 8.8 :`: .: . . . .

.`; nl~ p/ -31- ~
.
!, 5~3~46 `.
. 8.6 _ 4.4(~) -_ 3.8 (-~
. 3.68 (~) ~
: 3-38 (+~ -, ~ :
.~ 3.26 (~

' ;i . - 2 . 9 6 (+
,~ 10 - 2.88 (+~
. .; . .
., , ~ 2.79 (~
~;;,`~ 2-73 ~+~
2.66 (+) ~ .
2.60 (~
. .. . . .
.~ It is quite possible that not all these interference lines will appear in the X-ray diffraction diagram, particularly ....
.`~'; i~ the aluminosilicates are not fully crystallized. For this ~`;, reason, the d-values which are the most important for the characterizati.on of these types are identified by a "(~
Production conditions for aluminosilicate Im , ::~.~i. ;.
Precipitation: 2.985 kg of an aluminate solution of the composition 17.7% ~a20, 15.8% Al209, ~` 66.6% H20 0.150 kg o f sodium hydroxide 9.420 kg of water ~'.. ' ,~, .
2.445 kg of a 25.8~ sodium silicate solution of the composition: 1 Na20. 6 SiO2 (prepared as in I) Crys.tallization: 6 hours at 90C
3~ ~rying: 24 hours at 100C
,!,' Compos~itlon: 0;9 Naao . 1 Al209 . 2~04 SiO2 . 4.3 H20 21.6% ~120) .
` s. :
"~:' ' .:' - ':
~ m~p/ -32~

~L~58~

Vc~rcc oI Cry~ I Al-liznt:ion: Colnp:l.el:ely cry~t:alline :. Calclum bln(lin~
: power: 170 mg CaO/gm AS.
',:; ' ' ; , ...
"' .. , ` ~:
.....
~, :
:, .
..... .
.,; 10 ~:
~, . . :
~'''' ;'' ' .
, ~ ,.
,~,.................................................................... ..
.,, ` i `

.,.,., " , .
.... , ;, .
~l 20 :;`,'1' ~

~ i~ i ' "' ' ', ' ' '' '.' .

;.`~ ' `';' ~`.~.~, ` " , ' `. 30 '',''.' . ''.. ''~.':' :~.: , :-::
-i. ~ . ' m~ p / . - 3 3 ~
`''' ' .,`' ~:
: , . . . .

' ' , ' ' , ~ . ' . ' . !,, ,, . . , . ~ , ~ .

5~ 6 , . :
The distribution of the particle size deter~ined by sedi~enta-tion analysis was in the folloNing ran~e:
~40 ~ - 0~ The maximum range of the particle . .~...
~ ~10 ~ = 85~ to S5c,~ size distribution curve was ; ~ 8 ~ = 50% to 85~ situatad at 3 to 6 u.
The salt constituents contained in the detergents of the examples, such as sur~actants in salt form, other organic salts, as well as inorganic salts, were present as sodiu~ salt, unless explicitly stated otherwiseO This also applies to the .; ~ ...
10 precipitation inhibitors or chelating agents which are desig-nated for simplicity's sake as the corresponding acids. The designations and abbreviations used have the following meaning:
ABS the salt of alkylbenzenesulfonic acid with 10 to ~, 15, pre~erably 11 to 13 carbon atoms in the alkyl chain, ob-~ tained by condensation of straight-chain olefins with benzene r~ and sulfonation o~ the alkylbenzene thus obtained.
:,.
.~ ALKANE SULFONATE a sul~onate obtained ~rom para~fins with 12 to 16 carbon atoms by sulfoxidation.
FA-ESTER SULFONATE a sulfonate obtained from the methyl ester o~ a hardened tallow fatty acid by sulfonation with S03.

OL~FIN SULFONATE a sulfonate obtained from mixtures . - ' ~ ....o~ straight-chained non-terminal olefins with 12 to 18 carbon atoms by sulfonation with S03 and hydrolyzation of the sulfo-nation product with sodium hydroxide solution~ which consists substantially of alkene sulfonate and hydroxyalkane sulfonate, but also contains in addition small amounts of alkane di-, ,~.j,~, , .
~`~ sulfonates, OA + x EO or TA -~ x EO the addition products o~

3 ethylene oxide (EO) onto technical oleyl alcohol (OA) or tallow ,~ . .; .
~ atty alcohol (TA) (iodine number = 0.5), where the values for ~ .....
` x indicate the molar amount o~ ethylene oxide added onto 1 mol ,.i.:. ; .
,;,,. ~~ ~

.. ~ .

. ~.. . . . . . .
. ~ ., . . ~ .

.~05i8~D46 of alcohol.
T~-SULF~TE the salt o~ a sulfated,substantially ., _ ,' saturated fatty alcohol produced by reduction of the tallow ',"'~ fatty acid.
" .
' TA-EO-SULFATE the sulfated addition product of 3 ", . - ., ,~ ~ols of ethylene oxide onto l mol of tallow fatty"alcohol ~ . ~
,"~ CMC the salt of carboxymethyl cellulose ; . .
';, PERBORATE a product containing about lO~ acti~e oxygen, approximately of the following compositionO NaB02 .
~,, lO H202 3 H20 ','~ NTA the salt of nitrilotriacetic acid .:,.. , . :
~, HOSPHORIC ACID ESTER a reaction product of P205 ~ and an ethoxylated fatty alcohol :" FOAM INHIBITOR I a polymeric silicon-organic com-pound, so~called silicone oil -` FOAM INHIBITOR II an N-alkylated aminotriazine from .... . .
.~:, , .
~' the react,ion o~ oyanuric chloride w'lth mono or dialkyl amines ,, with 8 to 18 carbon atoms in the alkyl radical t.~,.' ; ' . ALUMINOSILICATE Im a microcrystalline alumino-;ri,~:, 20 silicate, prepared as described above, the percentages by weight '~`j"',!, being based on the anhydrous active substances '~
~ 'J AL A~l <~L _ 5IL~CAI~ a sQdium silicate with a ~,S?,` i . .
~, SiO2/Na20 weight ratio o~ 3,35:1 ~'t.' . .
' SOAP Cl2 22 or SOAP Cl6_18 salts of fatty acids - . _ ,. ~ ~: , - :
~ , with the indicated number of carbon atoms. ~
.. -, :
~'' The following examples 1 to lO (Table l~ show builder '' combinations which fall within the ~ramework of the invention ~ '~
,' and which can be used in the method of the invention.
~ . .. .
s -3S-,.'' ' .:
.` ' " ,:, .:`..................................................................... ;:
: ;
` .':. ,, ., ~ .

~ 58~
.
,,..................................................................... ~. .
TABLE ]-Component Example 1 2 3 ~ 5 ¦Aluminosilicate Im 1 --l~ ~l = 8.0 NTA 16.4 23.2_ 21,1 _ ~ 73.0 Sodium tripolyphosphatel70.0 1 46.323.4 11.919.0 `: L' I .. : .
~ ;Alkali metal silicate 6.6 7.3 6.3 5.9 __ --L----- _ . . .. . . . . _ _ _ _. . . _ . __ ~ TABLE 1 ~Continuation) r`' ¦Component Example ~
,i~ 10 ~ ,6 _ 7 8 1 9 1 10 t;'~ Aluminosilicate Im~ 15,0 7.7 17.8 , 35,5 29.2 i~ !N~A I 35.0 , 69,2 55.~ 35,0 56,8 ~.i .-.. _.... . _. __. ._ _L---------.---~ ------- ___ ______ __ i~ Sodium carponate 50.0 ¦ 23,1 26.8 __ __ ~.~ . , . _ _ _ _.. ... _ .. _ _ ... ......... .. . _ _ ._ _ _ _ _ .
~ IAlkali metal silicate __ ~ __ ~9.5 14.0 ~''' ' '.
The abo~e-mentioned builcler combinations are suitable as active combinations or concentrates and can be used as such or the preparation of wash liquors, but they can also be em-ployed as a part of a more comprehensive washing agent composi-i~.. ,., . : .:
tion formulation, None of the compounds used in the above-mentioned combination is ever available in practice completely anhydrous, `-although this would be theoretically possible. Accordingly, ,i "dry ~ormulations" are indicated in Table 1, that is for~ula-tions where the individual components calculated as dry sub-stance add up to 100~ by weight. Because of the water content ~, of the components, which is always found in practice, about . . ~ .
. 30~ to 36~o by weight of water must be added to these "dry - ` formulations" to obtain the total composition. While the water .~..................................................................... ;. .
`'"~ !, , '~'.

.:
., .
content naturally never goes below about 3~ by weight~ the ;. upper limit of 36~ by weight can be exceeded at random, de-pending on the requirements for the active substance concentrate.
Examples 11 to 20, as given in Table 2, are various formulations of washing agent compositions for textiles of the ..
. invention, where the builder combinations of Examples 1 to 10 ::
", ~
.. are i~proved by combination therewith o~ customary components ; of washing and cleaning agent compositions.
~ TABLE 2 :~ 10 Component Example '~ ;'~ 1 -~ 12 13 14 15 .. ABS ~.5 _ _ 4.2 , - : :
. ___ ~ __ _ _ ___ . _ __ __ ._ ~ . .
.. Alkane sulfonate _ 6.8 - ~ ----,. Ole~in sulfonate _ _ _ 2.1 _ . ,~......... ~ ___ __ _ . __ _ __ _ _ ~ _ .Fs-ester sulfonate L ~ _ 1.0 _ 7.4 . ~ :
TA-sul~at~ ~ .............. ---- = ~ _._-_-_ _ = 1.2~
;~. T~ ~ 14 EO 2.3 7.1 _ _ _ .:
~ ._ __ ___ ._.. ___. ...... ~ .. ,.. _.. _.. . ____ ____ ~ _ __._ I
.~TA ~ 11 EO . . ....... ... . . .... --. - - L
.~ TA ~ 5 ~0 1.2 2.8 1 - _ _ ::
:,. _ ____ ____. _ _ . .
20OA + 10 EO _ _3.7 _ _ ':' __.___.___. __. _ _ .. :
~ OA ~ 5 EO _ _ _ _1.2 ;~ _. _.__ _ _ . ___ .___ _ __ __ I .:
. o&p ~12-22 3.0 2.1 4.2 _ 3.1 I
:;:'~ioap Cl6-l8 _ 1.4 _ 1.3 _ ::.
~ . ~ ____ _ _ .. . _. . ._ ___.. __ _ _ _ ___ ___ _ , :, . ~gSiO3 1----------------_ ------- ---- _ __ ~ 1.8 _. .
..; Phosphoric acid~ester _ 2.5 _ 1.9 _ :. ~C 1.6 1.3 1.8 _ 1.2 ;.
~ ~ptical brightener 0.3 1 0.2 0.23 0.2 I

~. . _ __ _. _.. _ . _._ _ .___ _ ___ _._ _ _ _. ._ .
~ Foam Inhibitor I _ _ _ _ 0.1 ... ___ _.__ .__.. _ .. . ... .. . .... .... .... , . _____._ ~ ~
.~ Foam Inhibitor II _ _ _ 0.8 _ ,,, , _ . _.. _ .. _ ., .. _. . .. . . . . .. . ... _ _ _ ~ ; .,:
~. 30 Perborate 30~0 26,5 1 _ :
_ _ __.~
,: 3~- ; :
. 3~ .
...

: ::.

TABLE 2 (Continued) Component Example TABLE 2 (Continued) Component Example :~
;~l TABLE 2 ~ontinued) ; ~ Exa~ple ..~

, ~ . ..
Perborate 32.0 18,0 _ 1 25.0 ~ombination 6 - I 52.8 _ ~

ombination 7 1 32.2 1 - _ _ _ ~o~bination 8 - j 51.2 _ _ _ 'ombination 9 _ ¦ _ 45.7 _ .; ~ombination 10 _ I _ _ _ 67.5 Balance:

; ~a2S04 and water ~ _ . . _ . .:. .
.. .. . . .
. .;, ~
., :
~' In Examples 16 to 20, the addition o~ 4,2~ by weight ~' of hydroxyethane-l,l-diphosphonic acid has proved particularly advantageous.
' In Table 2 the percentages in the combinations 1 to ~- 10 relate likewise to the anhydrous formulation.
~' The ~ormulationsasindicated in Table 2 concern washing agent compositions which are provided for use as so-called all-purpose detergents. Examples 11 to 14, 16, 17 and ..... ..
;, 20 19 describe detergents particularly suitable ~or washing at ~ -high te~peratures (about 95C), while Examples 15, 18 and 20 describe detergents for washing at medium temperatures, for exampleg 60C. Naturally the detergents of the former group of Examples 11 to 14, 16, 17 and 19 can also be usled at lower te~peratures~ and the detergents o~ the latter group o~
~,: . ,.
~; Examples 15~ 18 and 20 can also be used at higher temperatures ;' or be used as low temperature detergents. But the low-te~pera-,...
`', ture detergents according to the invention contain generally higher surfactant portions than the above~described all-purpose ~,~ 3 detergents.
,....................................................................... . .
.~. ~ .

:. ," . . . . .. " . .

~5~ 6 ,.
.
~- In Examples 11, 12 17 and 20 the builder combina-,~, tions 2, 4, 8 and 10 respectively are combined with the partic-,. .
` ularly favorable surfactant combinations where nonionic com~
`~ pounds with 8 to 20 ethylene oxide units in t~ molecule are combined with nonionic compounds which contain 2 to 6 ethylene .. .. .
~;. oxide units in the molecule and where anionic tenides are also present in addition to the nonionic compounds .l Since the detergents of the examples can be produced . -,......................................................................... .
according to any method known in the industry, a detailed de-scription of the production has been foregone.
.-. i ., The preceding specific embodiments are illustrati~e of the practice of the invention, It is to be understood, however, that other expedients known to those skilled in the r,?~ ' :
art or disclosed herein may be employed without departing from ~: the spirit of the invention or the scope of the appended claims.
!i.; .',. ~
'r~ ,~;

''~r ~

~.'```'' ` ~ ' :
' . ,. ' , `
"', ;,` `, ' ' ' r ' "'`'.' `.'' ' `

~":
.3:..
:.: ,,.~. - .
.,.. :. ~ .

!. .:. ,` ~ , ,'`; ' ' !` ' " ' .
~,,..',. ~

~V, '' ''.;:, "

Claims (19)

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 com-prising the steps of contacting soiled textiles with an aqueous liquor containing from 0.2 to 10 gm per liter of compounds inhibiting alkaline earth metal ion precipitation on said soiled textiles as well as from 0.3 to 3 gm per liter of a surface-active component consisting of from 1 part by weight of nonionic surface-active compounds and from 0 to 3 parts by weight of anionic surface-active compounds, 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 hydrogen and from 8 to 18 carbon atoms ethoxylated with from 2 to 6 ethylene oxide units in a weight ratio of 10:0.2 to 2, 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 a builder combination of (1) at least one finely-dispersed, water-insoluble silicate compound containing at least some combined water and having a primary particle size of from 0.1 µ to 100 µ and a calcium binding power of 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2/nO)x . Me2O3 . (SiO2)y where M is a cation of the valence n, selected from the group consisting of sodium and potassium, 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) a combination of A) a water-soluble salt exchangeable with calcium of nitrilotriacetic acid, B) an inorganic phosphate capable of binding or sequestering cal-cium, and/or C) a wash alkali selected from the group con-sisting of an alkali metal carbonate and an alkali metal silicate, where the ratio by weight of component A) to components B) and/or C) is from 10:1 to 1:10, and the ratio by weight of component (1) to component (2) is 1:0.5 to 20;
as said compound inhibiting alkaline earth metal ion precipi-tation.

2. The method of claim 1 wherein y is a number from 1.3 to 4.

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

4. The method of claim 1 wherein said ration of component (1) to component (2) is 1:0.5 to 18.

5. The method of claim 1 wherein said ratio of component A) to components B) and/or C) is from 5:1 to 1:5.

6. The method of claim 1 wherein said component B
is employed in such an amount that the level of phosphorus in said aqueous liquor does not exceed 0.6 gm/liter.

7. The method of claim 6 wherein said level of phosphorus does not exceed 0.3 gm/liter.

8. The method of claim 1 wherein said component C) is an alkali metal condensed phosphate.

9. A composition for use in washing agent compo-sitions consisting essentially of (1) at least one finely-divided, water-soluble silicate compound containing at least some combined water and having a primary particle size of from 0.1 µ to 100 µ and a calcium binding power of 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2/nO)x . Me2O3 . (SiO2)y wherein M is a cation of the valence n, selected from the group consisting of sodium and potassium, x is a number of from .07 to 1.5, Me is a number selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, (2) a combination of A) a water-soluble salt exchangeable with calcium of nitrilotriacetic acid, B) an inorganic phosphate capable of binding of sequestering cal-cium, and/or C) a wash alkali selected from the group con-sisting of an alkali metal carbonate and an alkali metal silicate, where the ratio by weight of component A) to components B) and/or C) is from 10:1 to 1:10, and (3) a surface-active component consisting essentially of from 1 part by weight of nonionic surface-active compounds and from 0 to 3 parts by weight of anionic surface-active com-pounds, 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 hydrogen 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, where the ratio by weight of component (1) to component (2) to component (3) is 1:0.5 to 18:0.5 to 5.

10. The composition of claim 9 wherein y is a number from 1.3 to 4.

11, The composition of claim 9 wherein said silicate compound is crystalline,

12. The composition of claim 9 wherein said ratio of component A) to components B) and/or C) is from 5:1 to 1:5.

13. A washing agent composition consisting essentially of (I) from 5% to 40% by weight of a surface-active component consisting essentially of from 1 part by weight of nonionic surface-active compounds and from o to 3 parts by weight of anionic surface-active compounds, said nonionic surface-active compounds being a mixture of a compound having a labile hydrogen and from 8 to 15 carbon atoms ethoxylated with from a to 20 ethylene oxide units and a compound having a labile hydrogen 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;
(II) from 10% to 95% by weight of a builder component consisting essentially of (1) at least one finely divided, water insoluble silicate compound containing at least some combined water and having a primary particle size of at least 0.1 µ to 100 µ and a calcium binding power of 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (M2/nO)x . Me2O3 . (SiO2)y where M is a cation of the valence n, selected from the group consisting of sodium and potassium, x is a number of from 0.7 to 1.5, Me is a number selected from the group consisting of aluminum and boron, and y is a number from 0.8 to 6, and (2) a combination of A) a water-soluble salt exchangeable with calcium of nitrilotriacetic acid, B) an inorganic phosphate capable of binding or sequestering cal-cium, and/or C) a wash alkali selected from the group con-sisting of an alkali metal carbonate and an alkali metal silicate, where the ratio by weight of component A) to components B) and/or C) is from 10:1 to 1:10, and the ratio by weight of component (1) to component (2) is 1:0.5 to 20, and (III) from 0 to 50% by weight of at least one of the following: foam stabilizers or inhibitors, chemical bleaches as well as stabilizers and activators therefor, soil suspension agents, corrosion inhibitors, antimicrobial compounds, enzymes, optical brighteners, dyes and perfumes.

14. The washing agent composition of claim 13 wherein y is a number from 1.3 to 4.

15. The washing agent composition of claim 13 wherein said silicate compound is crystalline.

16. The washing agent composition of claim 13 wherein said ratio of component (1) to component (2) is 1:0.5 to 18.

17. The washing agent composition of claim 13 wherein said ratio of component A) to components B) and/or C) is from 5:1 to 1:5.

18. The washing agent composition of claim 13 wherein said component C) is an alkali metal condensed phosphate.

19. The washing agent composition of claim 13 wherein said component C) is an alkali metal carbonate.