CA1036455A - Washing compositions containing inorganic silicates and method of washing textiles - Google Patents

Washing compositions containing inorganic silicates and method of washing textiles

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Publication number
CA1036455A
CA1036455A CA 197628 CA197628A CA1036455A CA 1036455 A CA1036455 A CA 1036455A CA 197628 CA197628 CA 197628 CA 197628 A CA197628 A CA 197628A CA 1036455 A CA1036455 A CA 1036455A
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CA
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Grant
Patent type
Prior art keywords
water
washing
acid
group consisting
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA 197628
Other languages
French (fr)
Inventor
Manfred Rostek
Milan J. Schwuger
Heinz Smolka
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites

Abstract

ABSTRACT OF THE DISCLOSURE
A method of washing soiled textiles, wherein the soiled textiles are immersed in an aqueous liquor which con-tains at least one compound inhibiting alkaline earth metal ion precipitation on said soiled articles comprising using finely-dispersed, water-insoluble silicate compounds 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 gallon of the valence n, exchangeable with calcium, x is a number of from 0.7 to 1.5, Me 18 a member selected from aluminum and boron and y 18 a number of from 0.8 to 6, as said compound inhibiting alkaline earth metal ion precipita-tion; as well as washing compositions containing said silicate compounds.

Description

3645~

As known, the detergents used in the household, in commercial establishments and in industry, fre-quently contain large quantities of condensed phosphates, particularly tripolyphosphate~. These are provided to sequester the hardness formers o~ tap water and are responsible to a great extent for increasing the cleaning power o~ the capillary-active was~ing substances. The phosphorus content of these agents has been critlcized 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,h~ue great in-fluence on the eutrophication of the waters) and is said to lead to an increase of the growth of algae and of oxygen con-sumption. It has therefore been tried to eliminate phosphate from the washing and cleaning processes or fxom the agents used for this purpose, or at least to substantially reduce its proportion, In DOS (Ger~an Published Patent Application) 1,617,05a, it has already been suggested to use flat fabrics or sheets of water-insoluble cellulose derivatives, particularly phosphoryl-ated cotton, during the washing process for softening the water. But this proposal does not represent a technically feasible solution of the problem since too large amounts of phosphorylatad cotton have to be added to bind the hardening constituents of the water. The other cellulose derivatives mentioned in the same proposal, namely sulfethoxy cellulose, carboxymebhyl cellulose and the succinic acid half esters of cellulose, have only a weak calcium binding power and are therefore hardly suitable for use i~ practice .
=l=

69~5S
In DOS 2,055,423, water-inæoluble cation-exchanging polymers which are insoluble in water and alkaline solutions are suggested ~or the same purpose, such as cross-linked co-polymers of polyacrylic acid or poly~ethacrylic acid with di-; vinyl compounds, for example divinyl benzene, as well as their sulfonation products mese are used in powdered to granu-lar form (grain size 0.22 to 1.2 mm). They are either added directly to the washing compositions or they are filled first into water-permeable containers or bags and placed in this form in the wash liquor, But it can be shown experimentally that the ion exchangers packed in containers, though they can bind the hardening constituents o~ the wash liquor, albeit at a slower rate, have no washing effect in this ~orm, not even if a good circulation through the exchanger container is ensured.
A satis~actory soil-releasing effect can only be observed if the exchanger particles can come in direct contact with the textile fib~r during the washing process, that is, if the powdered to granular material is added directly to the w~shing composition or to the wash liquor, But this procedure has a number o~ serious advantages if the e~changer resins indicated in DOS 2,055,423 are used because exchanger particles which are trapped in the textile material are no longer washed out completely during the following rinsing cycle. Rather, they remain on the textile ~terial as impurities and become in-separately cemented with the ~iber during the following heat treatment, for example, hot drying, hot mangling or ironing In ~ummation, the washing effect of these polymers is relatively low and their use in the wash liquor brings hardly any advan-tages co~pared to an arrangement of the exchanger in a series-connected water softening plant.

~036~SS
An object of the present invention is the solu~ion of the above-outlined problem of finding a non-polluting washing method which does not have the above-described in-conveniences and which particularly does not burden the waste water with phosphate.
Another object of the present invention is the de-velopment in the process of washing soiled textiles by con-tacting soiled textiles with an aqueous solution containing a water softening agent for a time sufficient to disperse or dissolve the soil from said soiled textiles into said aqueous solution, separating said aqueous solution and recovering said textiles substantially soil-free, o~ the improvement which consists of using at least one finely-~ispersed, water-insoluble silicate compound contain-ing 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 cal-cium, 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.~ to 6, as said water softening agent.
A yet further object of the present invention is the development of a detergent system for washing soiled textiles comprising the above ~ater-insoluble silicate compound and a low to zero phosphate textile detergent These and other objects of the invention will become more apparent as the description thereof proceeds.

~3~i45S

The invention concerns a method for washing or bleaching textiles, ~y treating these textiles with a liquor which contains sub-stances that are capable of binding the hardening constitu-~nts OL ~he-water. The method concern~ the use of a finely-- dispersed~ water-insoluble æilicate compound during the washing process and in connection with low to zero phosphate textile det~rgent~. It is characterized in that at least one finely-dispersed, water-insoluble silicate compound containing co~-i-0 bined water in the given case, having a calcium binding power of at least 50 mg CaO/gm of anhydrous active substance and the general formula (on the anhydrous basis) (M2/n)x Me203 ~si2)~
~here 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 i~ a number ~rom 0.8 to 6, preferably from 1.3 to 4, is suspended in the ~queous washing liquor.
The calcium binding power of the silicate compounds of the invention can be as high as 200 mg CaO/gm of anhydrous active substance (AS) and preferably is in the range of lOO;to 200 mg CaOjgm AS.
The cation M e~ployed is preferably sodium. HoweverJ
the same can also be totally or partially replaced by other cations exchangeable with calcium,such as hydrogen, lithium, potassium, &mmonium or magnesium, as well as by the cations of water-soluble organic bases, for example, by those o~ primary, secondary or tertiary alkylamines or alkylolamines with not more than 2 carbon atoms per alkyl radical, or not more than 3 carbon atoms per alkylol radical.

=4=

1036~S5 These compounds will hereafter be called ~alumino-silicates~ for simplicity's ~ake Preferred are sodium alumino-silicatès A11 data given for their production and use also appl~i~t~ the cther co~pounds claimed ~ he above-defined aluminosilicate~ can be produced synthetical~ in a simple manner, for example, by reacting watex-soluble silicates with water-soluble aluminates in the presence of water. To this end aqueous solutions of the start-ing materials can be mixed with each other, or one component ; 10 which is present in solid ~orm can be reacted with another component which is present as an aqueous ~olution. The de-sired aluminosilicates can also be obtained by mixing both solid components in the presence of water. Aluminosilicates can also be produced from Al(OH)3, A1203 or SiO2 by reaction with alkali metal silicate or al~ali metal aluminate solutions. Finally, such substance~ 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 I ~he cation-exchanging alumino~ilicate~ to be used according to the invention are only formed if special precipi-tation conditions are maintained, otherwise products are formed which have no, or an. inadequate,calcium exchanging power. m e calcium exchanging power of at least 50 mg CaO/gm of anhydrous active substance (AS) is critical to the present process. If aluminosilicates are employed with below the critical limit of calcium exchanging power, very little if any soil removal from the soiled ~xtiles is effected in the absence of other types of calcium sequestering or precipitating agents. The prod-uction of useable aluminosilicates according to the invention is described in the experimental part.

=5=

~3~455 The aluminosilicates in aqueous suspension produced by precipitation or by tran~formation in finely~dispersed form according to other methods can be tranæformed from the amorphous into the aged or into the crystalline state by heating the suspension to temperatures of 50 to 200C, How-ever, there is hardly any difference between these two forms as far as the calcium binding power is concerned, Aside from the drying conditions, the calcium binding power of the alumino-silicates is proportional to the amount of aluminum contained therein with reference to the amount of silicon, Nevertheless, the crystalline aluminum silicates are preferred for the purpose of the invention. The preferred calcium binding power, which is in the range of 100 to 200 ~g CaO/gm AS, is found primarily in compounds o~ the composition:
0.7 to 1.1 Na20 . A1203 . 1,3 to 3.3 SiO2 This summation formuIa comprises two types of dif-ferent crystal structures (or their non-cr~stalline 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.~ to 3.3 SiO2 The different cryætal structures can be seen in the X-ray dif~raction diagram. The d-values found are given in the examples in the description of the production of the aluminosilicates I and II.
The amorphous or crystalline aluminosilicate contained in the aqueous suspenslon can be separated by filtration from the remaining aqueous solution ~nd be dried at temperatures of 50 to 800C~ for example. Depending on the drying condi-tions, the product contains more or les~ combined water, =6=

`~

'1(~3~
Anhydrous products are obtained by drying at 800C. If we want to remove the water completely, this can be done by heating for 1 hour to 800C. This i8 the way the AS contents of the aluminosilicates are also determined.
Such high drying temperatures are n~t recommended ~or the aluminosilicates to be used according to the inven-tion, preferably the temperature should not exceed 400C. It is of particular advantage that even produc~s dried at sub-stantially lower temperatures of 80 to 200C, for example, until the adhering liquid water is removed, can be used for the purposes of the invention The aluminosilicates thus produced, which contain varying amounts of combined water, are obtained after the disintegration of the dried filter cake, as fine powdersiwhose primary particle size does not exceed 0.1 mm, but is mostly lower and ranges do~n to dust fineness, for ex-ample, to O.l U, 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 50 to l~u are obtained Of particular advantage are aluminosilicates having at least 80% by weight of particles o~ 10 to O.Ol~u,prefera-bly 8 to 0.1_~. These aluminosilicates preferably contain no primary or secondary particles above 40~ . As far as the products are crystalline, they are "micro-crystalline "
The ~ormation of smaller 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 sub~ected to great shearing forces If crystalline =7=

~ 3645S
alumlnum 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, undeslred agglomeration of crystal particles can occur during the dry~ng, so that it is advisable to re~ove these secondary particles in a suitable manner, for example, by air sifting Aluminosilicates obtained in coarser form, which are ground to the de~red 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, ~or example, in Ullmann, "Enzyklopadie der technischen ; Chemie" vol. 1, 1951, p. 632 to 634.
~ From the sodium aluminosilicates, aluminosilicates o~ other cations, for example, those of potassium, magnesium or water-soluble organic baees can be produced in a simple ; manner by the exchange o~ bases. The use of these compounds instead o~ ~he ~odium aluminosilicates may be of advantage if ~ a special effect i8 tolbe achieved by the supply of the said ; cations, ~or example, if the state of dissolution of different surface-actlve compounds simultaneously present in the compo-sition is to be influenced.
These prepared aluminosilicates, that is, produced prior to their use, are used for the purposes of invention.
The amount of aluminosilicate required to achieve a ~ood washing ef~ect depends, on the one hand~ on its calcium binding 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 advlsable to select the amount of alu~inosilicate so that the residual hardness of t~é water does not exceed 5~dH

-8=

" ......
(corresponding ~o 50 ~g CaO/l)J preferably 0,5 to 2dH (cor-responding to 5 to 20 ~g CaO/l), In order to obtain an optimum washing ef~ect, it is advisable, particulary for greatly soiled textiles, to use a certain excess of alumino-silicate, in order to bind completely or partially the harden-ing constituents contained in the released soil. The concen-tration of the aluminosilicates can thus ~e in the range from 0.2 to 10 gm AS/l, pre~erably 1 to 6 gm AS/l.
It was also found that the dirt can be removed much faster and/or more completely i~ another substance is added to the wash liquor which has a sequestering and/or precipitating ef~ect on the calcium which is contained in the water as a hard-ening substance. Suitable as sequestering agents ~or calcium for the purposes of the invention are also substances with such a low sequestering power that they were not considered heretofore as sequestering agents for calcium. However, these compounds frequently have the capacity of delaying the precip-it~tion o~ calcium carbonate from aqueous solutions.
Preferably, amounts o~ sequestering or precipitating agents o~, for example, 0.05 to 2 gm/l, are added to accelerate or improve the removal 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 are used, their amount should be so selected that the phos-phorus load of the sewage is much less than with the presently used triphosphate-based detergents.
Generally speaking, the compositions for general use in washing, rinsing andbleaching agen-t compositions o~ the invention are those washing auxiliary compositions consisting essentially of (a) from 5~ to 95% by weight of at least one ~3~;4S5 compound capable of sequestering calcium or inhibiting the precipitation of calcium carbonate selected from the group consisting..of organic salts and inorganic salts, and (b) from 95~ to 5% by weight of a finely-dispersed, water-~nsoluble silicate compound c~ntaining at least some combined water and having a calcium binding power of at least 50 mg Ca~/gm of anhydrouæ active substance a.nd the formula on the anhydrous basis (M2/n )x ^ Me23 (si2 )y where M is a cation of the valence n, exchangeable with cal-cium, x is a member of from 0.7 to 1,5, Me is a member selected from the group consisting o~ aluminum and boron, and y is a number from 0.8 to 6.
The sequestering precipitating agents include thoseof an inorganic nature, such as alkali metal~;salts of condensed phosphates, like pyrophosphate, trlphosphate, higher polyphos-phates and metaphosphates, Organic co~pounds which are used as sequestering or p~ecipitating agents for calcium are the polycarboxylic acids, hydro~ycarboxylic acids, aminocarboxylic acids, car-boxyalkyl ethers of alkanepolyols, polyanionic polymers, par-ticularly the polymeric carboxylic acids and the phosphonic acids, these compounds being used mostly in the form of their water-soluble salts.
Examples for polycarboxylic acids are the alkane polycarboxylic acids having from 2 to 20 carbon atoms, and the alkene polycarboxylic acids having ~rom 4 to 10 carbon atoms, such as the dicarboxylic acids of the general formula HOOC - (CH2)n - COOH
where n is an integer ~ro~ O to 8, as well as maleic acid~

=10=

~364~i5 fumaric acid, methylene~alonic acid, citraconic acid, mesaconic acid~ itaconic acid, n~n-cyclic polycarboxylic acids with at least 3 carboxyl groups in the molecule, like tricarballylic acid, aconitic acid, ethylene tetracarboxylic acid, 1,1,3,3-propane-tetracarboxylic acid~ 1,1,-3,3,5,5-pentane-hexacarboxylic acid, hexane-hexacarboxylic acid, cyclic di- or polycarboxylic acids, such as cyclopentane-tetracarboxylic acid, tetrahydrofu-ran-tetracarboxylic acid, cyclohexane~hexacarboxylic acid, phthalic acid, terephthalic acid, benzene tri-, tetra- or pentacarboxylic acid aæ well as mellitic acid.
Examples for hydroxyalkanemono or polycarbox~lic acids and hydroxybenzenemono or polycarboxylic acids are glycolic acid, lactic acid, ~malic acid,tartronic acid, methyl-tartronic acid, gluconic acid, glyceric acid, citric acid, tartaric acid, salicylic acid.
Examples for aminocarboxylic acids are glycine, glycylglycine, alanine, aspargine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxyethyl-iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethyl-ethylene-diaminetriacetic acid, diethylenetriaminepentaacetic acid,as well as higher homologs which can be prepared by polymeri-zation o~ a N-aziridyl carboxylic acid derivative, ~or example, of acetic acid, of succinic acid, of tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10,000 with chloracetic acid salts or bromacetic acid salts.
Examples for carboxyalkyl ethers are 2,2-oxydisuccinic acid and other carboxyalkyl ethers with alkanepolyols and hy-droxya~kanoic acids, particularly polycarboxylic acids contain-ing carboxymethyl ether groups which include corresponding ~036~5 derivatives of the following polyhydric alcohols or hydrocar-boxyllc acids, which can be completely or partly etherified with glycolic acid, such as ethylene glycol, di- or tri-oxyethylene glycols, glycerin3 di- or triglycerin, glycerin monomethyl ether, 2,2-dihydroxymethyl-propanol, l,l,l-tri-hydroxymethyl-ethane,l,1,1-trihydroxymethyl-propane, erythrite, pentaerythrite, glycolic acid~ lactic acid, tartronic acid, methyltartronic acid, glyceric acid, erythronic acid, m~lic acid, citric acid, tartaric acid, trihydroxyglutaric acid, saccharic acid, mucic acid In addition, the carboxymethyl ethers of su~ar, starch and cellulose are mentioned as trans-ition types ~o the polymeric carboxyllc acid8.
Among the polymeric carboxylic acids, the polymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalon~c acid, citraconic acid, etc., the copolymers of said carboxylic acids - with each other or with ethyl~nic-unsaturated compounds, like ethylene, propylene, isobutylene, vinyl fllcohol, vinyl~ethyl~
~ ether, furan, acrolein, vinyl acetate, acrylamide,a~ylonitrile, 20 methacrylic acid, crotonic acid, etc., such as l:l copolymers o~ maleic acid anhydride and ethylene or propylene or furan, play a particular part.
Other polymeric carboxylic acids ~ of the type of polyhydroxypolycarboxylic acids or polyaldehydropolycarboyxlic ac~ds are substances substantially composed of acrylic acid and acrolein units or of acrylic aci~ and vinyl alcohol-units, which can be obtained by copolymerization of acrylic acid and acrolein or b~ polymerization of acrolein and subsequent Canniz-zaro reaction, if necessary, in the presence of formaldehyde.

=12-3645~;
Examples of phosphoru -containing organic sequester-ing agents are the alkanepolyphosphonic acid~, aminoalkane polyphosphonic acids, hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids, such as t~e co~pounds methane-diphosphonic acid, propane-1,2,3-triphosphonic acid, butane-- 1~2,3,4-tetraphosphonic acid, polyvinyl phosphonic acid, l-amino-ethane~l,l diphosphonic acid, l-amlno-l-phenyl-methane-l,l-di-phosphonic acid, amino-trimethylenephosphonic acid, methyl-amino-d~ethylenephosphonic acid, e~hyla~inodimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, l-hydroxy-ethane-l,l-diphosphonic acid, phosphonoacetic acid, phosphono-propionic acid, l-phosphonoethane-l,~-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 2-phosphonobutane-1,

2,4-tricarboxylic acid, 2-phosphonobutane-2~3,4-tricarboxylic acid, as well as copolymers of vinyl phosphonic acid and acrylic acid By using the above-described aluminosilicates ac-cordlng to the invention it is readily possible, even when using phosphorus-containing inorganic or organic sequestering or pre-cipitating agents for calcium~ to keep the phosphorus contentof the wash liquors at a maximum of o,6 gm/l, preferably at a maximum of 0 3 gm/l, But it is also possible to effect the method of the invention in the absence of phosphoru~-containing compounds with good results.

.

~Q36455 The field of application of the invention is the washing and bleaching of textiles of all kinds in industry, in commercial laundries, and in the household.
The textiles to be washed can consist of various fibers of` natural or synthetic origin. These include cotton, regenerated cellulose or linen, as well as textiles which contain highly processed cotton or synthetic che~ical fiberæ, like polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or po~yvinylidene chlor~de fibers. The detergents according to the invention can also be used for washing synthetic fiber-cotton blends o~led "wash and wear", occasionally also "no-iron" fabrics.
When washin~ by using cleaning liquors containing aluminosilicates in aqueous suspension, the washing or clean-ing can be improved by co~on ingredients of these wash liquors These include, for example, surface-active compounds, surface-active or non-surface-active foam stabilizers or in-hibitors, te~tile softeners, neutral or alkaline-reacting builder salts, che~ical bleaches, as well as stabilizers and/or activators for the latter~ soil suspension agents, corrosion-inhibitors, anti~icrobial substances, enzymes, ; brighteners, dyes and perfumes.
When using one or several of the above-mentioned substances, normally contained in wash liquors, the follow-ing concentrations are preferably maintained:

=14-~036~55 O to 2,5 g~jl of æurface-active compounds - 0 to 6 gm/l of builder salts O to 0.4 g~/l of activated oxygen or equivalent amounts of activated chlorine as a b}ea h.
The p~-value of the liquors can be between 6 and 13, pre~erably between 8.5 and 12, depending on the type of tex-ti}e to be washed.
~ or a long time, atte~pts have been made to find a su~table substitute for phosphates which can not only bind calclum but ~hich are also biode~radable in sewage. Various organic compounds have, there~ore, been suggested as pho phate substitutes The technical teaching of the invention of using for this purpose water-insoluble cation-exchanging alumino-- silicates is ~herefore a complete abandonment of the ~eneral direction in whlch the industry has worked It is particularly surprising that the water-insoluble aluminosilicates used in the $nvention are completely washed out from the fabrics. The use of the aluminosilicates ~eans a relief of the sewage in two respects. The amounts of phosphorus arriving in the sewage are greatly reduced or completely eliminated, and the aluminosilicatcs require less oxygen for biological degradation.
They are of a mineral nature, settle gradually in the clari~ying plants or in natural waters and thus meet the ideal requ~sites of a phosphate substitute.
But they are also superior to other suggested phosphate substitutes in their washing action In particu-lar, they absorb ~olored soil,and thus save on chemical bleaches =15=

lQ36~55 The invention concerns,furthermore, agents for carry-ing out the claimed met~lod which contain calcium-binding sub-stances. These are characterized in that they contain, in addition to at least one washing, ~leaching or cleaning in-organic or organic compound, the above-mentioned alumino-silicates aæ a calcium-binding compound. Beyond that these agents can contain other additives which are mostly present in sm~ll amounts.
The aluminosilicate content of these agents can be in the range of 5% to 95~, pre~erably 15~ to 60%.
The agents according to the invention can also con-tain sequestering agents, or precipitating agents ~or calcium, whose action can be recognized at contents of 2% to 15~, depending on the chemical nature o~ the agent.
The amount o~ inorganic phosphates and/or organic phosphorus compounds in the agents according to the invention should not bc~;greater than corre~ponds to a total phosphorus content o~ the agent of 6%, preferably 3~
All these percentages are percentages by weight, they relate to the anhydrous active substances (AS).

=~6=

645~;
, .. . .. . .
e wa3hing or bleaching co~pounds con-tained in the washing agents comprise, for ex-.ample., surface-active compounds, surface-active or non-surface_actlve foa~ stabilizers or inhibitor~, textile soften~
~: ~ers~ neutral orlalkal~ne-reacting builder salts, chemical bleaches, as well as stabilizers and/or activators for the atter. Other additives, which are mostly contained in small -qua~titiesJ are for example~ corrosion inhibitors, antimicro-b~al substances, soil suspension agents, enzymes, brighteners, : 10 dyes and perfu~e~.
The composition of typical textile washing agents to be used 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 amphoteric surface-active compounds 5% to 70% of aluminosilicates (related to AS~
2% to 45~ of sequestering agents ~or calcium O to 50~ of wash alkalies not capable o~ sequestra-tion (alkaline builder salts) 0 to 50~ of bleaches as well as other additives mostly contained in detergents in small quantities A list o~ substances suitable for use in the agents according to the invention follows:

~(~364~i~
The surface-active compounds or tensides contaln ln the molecule at least one hydrophobic organlc moiety and one water-solubilizlng, anionic, non-lonic or amphoteric group. The hydrophobic moiety is mostly an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and particularly 12 to 18 carbon atoms or an alkyl aromatic radical, such as alkylphenyl, 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 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 sulfon-ation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates whlch are obtained from alkanes by sulfo-chlorination or sulfoxidation and subsequent hydrolysis or neutrali2ation or by bisulfite addition to olefins. Other suit-able tensides o~ the sulfonate type are the esters of ~-sulfofatty acids, for example, the ~-sulfonic acids of hydrogenated methyl or ethyl esters of coconut, palm kernel 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 secondary alcohols. Also suitable are sulfated fatty acid al-kanolamides, sulfated fatty acid monoglycerides or sulfatedreaction products of l to 4 mols of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

db/~``g -18-`` ~@3~;~5~i Other suitable anionic tensides are the fatty acid esters or amides of hydroxy- or amino-carboxylic acids or sulfonic acids, such as the fatty acid sarcosides, fatty acid glycolates, fatty acid lactates, fat~y acid taurides or fatty acid iso-ethionates.
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 tri-ethanol amine.
Sui~able non-ionic surface active compounds or tensides are the addition products of 4 to 40, preferably 4 to 20 mols of ethylene oxide to 1 mol of a fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amine or alkanesulfonamide. Par-ticularly important are the addition products of 5 to 15 mols of ethylene oxide to coconut fatty alcohols or tallow fatty al-cohols, to oleyl alcohol or to secondary alkanols with 8 to 18, preferably 12 to 18 carbon atoms, as well as monoalkylphenols or tialkylphenols with 6 to 14 carbon atoms in the alkyls. In ad-dition 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 interest, particularly if they are used together with water-soluble non-ionic or anionic tensides.
Furthermore, the water-soluble addition products of ethylene-oxide to polyoxypropylene glycol containing 10 to 100 propylene glycol ether groups (Pluronics ~ ), to alkylenedia-minepolyoxypropylene glycol (Tetronics ~ ), and to alkylpoly-oxypropylene glycols with 1 to 10 carbon atoms in the alkyl chaln, can also be used where the polyoxypropylene glycol chain acts as a hydrophobic radical.
Non-ionic tensides of the type of the amine oxides or suloxides can also be used.

db/ ~ ~ -19-... . ... . . . .

The foamlng power o~ ~ ide can be lncrea~ed or re-duced by combina~ion of suitable tenside types. A reduction can also be achieved by additions of non-surface-active organic substances.
Suitable foa~ stabili~ers, particularly in tensides of the 8ulf onate or sulfate type, are surface-active carboxy or sul-fobetaines, as well as the above-named non-ionics of the alkylo-lamide type. Moreover, fatty alcohols or higher terminal diols have been suggested for this purpose.
A reduced foaming power, that is desirable for the use in s washing machines, is often attained by combination of different tenside types, such as of sulfates and/or sulfonates with non-ionics, and/or with soaps. In soaps, the foam inhibition increases with the degree of saturation and the number of carbons in the fat-ty acid residue. Soaps derived from saturated C20 24 fatty acids have been proven good as foam inhlbitors.
The non-tenside foam inhibitors included N-alkylated amino-triazines, optionally containing chlorine, which are obtained by the reaction of 1 mol of cyanuric acid chloride with 2 to 3 mols of a mono- and/or dislkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl radicals. Similarly effective are propoxylated and/or butoxylated aminotriazines, such as, products that are ob-tained 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 oxide derivative.
Likewise suitable as non-tenside foam inhibitors are water-in~oluble organic compounds, like paraffins, or halogenated paraf-fins with melting points below 100C, aliphatic 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 resi-dues, at least 18 carbon atoms (sucl `~ db/~ ~ -20-, . . .

f -L()364SS
as triglycerldes or fatty acid/fatty alcohol esters). These compounds can be used to reduce foaming, particularly in com-binatlons of tensides of the sulfate and/or sulfonate type with soaps.
Particularly low-foaming non-ionics, which can be used elther alone or in comblnatlon with anionic, amphoteric and rlon-ionic tensides, and which reduce the foaming 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 products of ethylene oxide to polyoxypropylene glycols and to alkylene-diamine polyoxypropylene glycols or to alkyl polyoxypropylene ~lycols having 1 to 10 carbons in the alkyl.

db/~ ~ -21-, .. .. ~ . . .

- ~364SS

Weakly acid, neutral or alkallne~reacting inorganic or organic salts can be used as builder salts Suitable weakly acid, neutral or alkaline-reacting salts for use according to the invention are, for example, the bicarbonates, carbonates, borates or silicates o~ the alkali metalæ, 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 benzenesul-10 - fonic acid~ toluenesulfonic acid or xylenesulfonic acid, water-soluble salts of sul~oacetic acid, sulfobenzoic acid or of sulfodicarboxylic acids.
The compounds mentioned above as sequestering or pre-cipitating agents for calcium are suitable as builder salts.
They can, therefore, be present ln the agents according to the invention in larger quantities than is necessary to perform their function as sequestering or precipitating compounds for calcium.
The individual components of the products used as textile washing 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 o~ the preparation is mostly in the range of 7 to 12. Fine washing agents show mostly a neutral to weakly reaction (pH
value - 7 to 9.5) while soaking agents, prewashin~ agents and boiling washing agents are more alkaline (pX value =
9 5 to 12, preferably 10 to 11.5.

=22=

3~5S
Among the compounds servlng as bleachlng agents and releasing Hz02 in water, sodium perborate tetrahydrate (NaB02.
H203. 3 H20) and the monohydrate (NaB02. ~22) are of partlcu-lar importance. But also other H202 releaslng borates can also be used, such as perborax Na2B407 . 4 H20. These compounds can be replaced partly or completely by other carriers of active oxygen, particularly by peroxyhydrates, such as peroxycarbonates, (~a2C03 . 1.5 H202), peroxypyrophosphates, citrate perhydrates, urea-H202 compounds, as well as by H202-releasing peracid salts, such as Caroates (KHS05), perbenzoates or peroxyphthalates.
It is recommended to incorporate water-soluble and/or water-insoluble stabilizers for the peroxy compounds together with the latter in amounts of 0.25% to 10% by weight. Water-insoluble stabilizers, which a~ount to 1% to 8%, preferably 2%
to ?% of the weight of the entire preparation are, for example, the magnesium having a MgO: SiO2 ratio of 4:1 to 1:4, prefer-; ably 2:1 to 1:2, and particularly l:l, which are mostly obtained by precipitation from aqueous solutions. In their place, other alkaline earth metal, cadmium or tin silicates of corresponding compositions are also usable. Also hydrous oxides of tin aresuitable as stabilizers. Water-soluble stabilizers, which can be present together with water-insoluble stabilizers, are mostly the organic 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 order to obtain a ~atisfactory bleaching effect when washing at temperatures belo~ 80C, particularly in the range of 60 to 40C, activator-containing bleaching components are preferably incorporsted in the preparations.

dbt~J~ -23-. Certain N-acyl and/or O-acyl compounds forming, with H202, organic per acids serve as activators for per 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'-tetraacylated amines, such as N,N,N',N'-. tetraacetyl-methylenediamine, N,N,N',N'-tetraacetyl-ethylene-diamine, 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-methoxybenzamide, the N-acylated cyclic hydrazides, acylated triazoles or urazoles, such as monoacetyl maleic acid hydrazide, the O,N,N-trisubstituted hydroxylamines, such as O-benzoyl-N,N-succinyl-hydroxylamine, O-acetyl- N,N-succinyl-hydroxylamine, O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine, O-p-nltrobenzoyl-~,N-succinyl-hydroxylamine and . ~ ' .

. dbt~ ~ -24-1(~36~55 0,N,N~triacetyl-hydroxylamine, the N,N'-diacyl-sulfuryl-amides, such as N~N'-dimethyl-N~N'-diacetyl-sulfurylamide, and N,N'-diethyl-N,N'-diethyl-N,NI-dipropionyl-sulfuryl amide, the tri-acyl cyanurates, such as triacetyl cya~urate or tribenzoyl cyanurate, the carbo~ylic acid anhydrides, such as benzoic : acid anh~dride, 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 exa~ple the compounds 1,3-di~ormyl-4,5-di-acetoxy-im~dazolidine, 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 ~lycoluril,thediacylated 2,5- diketopiperazines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-376-dimethy1-2,5-diketo-piperazine,~he ac~lated or benzolylated products of propylene-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 derivative3, and the sodium salts of p-ethoxycarbonyloxy)-benzoic acid and p-(propoxycarbonyloxy)-benzene sulfonic acid =25=

f ~36~5S
The activated chlorlne compounds servlng a~ bleaching agents can be of an inorganic or organlc nature.
~he inorganic active chlorine compounds include alkaline metal hypochlorites, which can be us2d particularly in the form of their mixed salts or addition compounds with orthophosphates or on condensed phosphates such as with alkali metal pyrophos-phates a~d polyphosphates, or with alkali metal silicates. If the washing agents and washing assistant compositions 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 chlo-! rine atoms are linked to a nitrogen atom, the third valence of the nitrogen atoms leading preferably to a negative group, par-ticularly to a C0- or S02-group. These compounds include di-chlorocyanuric acid and trichlorocyanuric acid or their salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydan-; toins and chlorinated melamines.
The preparations according to the invention can further-more contain soil suspension agents or dirt carriers, which keep the dirt released from the fibers in suspension in the liquor and 90 prevent graying. Suitable compounds are water-soluble colloids, mostly of an organic nature, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts o~ ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are al80 suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned ~tarch products can be u~ed, for example, degraded starches, aldehyde starches etc. Polyvinyl pyrrolidone can also be used.

db ~ ~ -26-, .. .

~36~55 The enzyme preparations to be used are mos~ly a mix-ture of enzymes wlth different effects, such as pro~eases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerages, lyases, transferases, des-molases, 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, per-compounds, and anionic tensides and are still effective at temperatures up to 70C.
Enzyme preparations are marketed by the manufacturers mostly as aqueous solutions of the active substances or as pow-ders, granulates or as cold-sprayed products. They frequently 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 water-of-crystalliza~ion-containing salts in their own water-of-crystallizatlon.
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.

db / ~ - 2 7-~, ... ,. V - ~ .

36~55 The washing agents can contain optlcal brig~ltener~ such as those for cotton, particularly derivatlves of diaminostllbene-disulfonic acld or its alkali metal salts. Sultable are, for example, salt6 of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilbene-2,2'-disulfonic acid or similarly compound6 which have instead of the morpholino group, a di-ethanolamino group, a methylamino group or a 2-methoxy-ethylamino group. Brighteners 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-chloro-phenyl)-2-pyrazoline, as well as compounds of similar com-position which have instead of the sulfamoyl group, for example, the methoxycarbonyl group, the 2-methoxyethoxycarbonyl group, 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-benzimi-dazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)~ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can also be used as polyamide brighteners. Brighteners for polyester and poly-smide fibers which can be used are the compounds 2,5-di-(2-benzoxazolyl)-thiophene,2-(2-benzoxazolyl)-naphtho-~2,3-b]-thiophene and 1,2-di-~5-methyl-2-benzoxazolyl)-ethylene. Further-more, 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 brighteners can likewise be used.

db~pP~ -28-~ . ~ t ~36~5~
Of great practical interest are agents according to the invention of powdered to granular consistency ~hich can be produced according to any method known in the art Thus, for example, the powdered aluminosilicates can be mixed in a simple manner with the other components of the wash~ng agent, while spraying oily or pasty products, such as non-ionics, onto the powder. Another production possibil-ity consists in incorporating the powdered aluminosilicates into the other components of the detergents in the form of an aqueous slurry which is then transformed into a powder by crystallization or by heat-drying to remove the water. After heat-drying, for example, on cylinders~or in atomizing towers, heat-sensitive and moisture-sensitive components can then be incorporated, such as bleaching components and activators ~or the latter~ enzymes, microbial substances, etc.

=29=

- 1~3~ ~ ~ 5 The following specific embodiments are illustrative i - o~ the lnvention without being limita~ive in any respect, E X A M P L E S
., - Fi~t, the production of the finished alu~inum sil-lcates is described, for which no inventlon is claimed. .
PROCESS COMDITIONS
. .,. _ .............. --- The aluminate solu~ion, diluted with deionized water was ~ixed in a vessel of 15 liter capacity, under vigorous - stirring ~ith the silicate solution. Both solutions were at , ~0 roo~ temperature. An X-ray amorphous sodium aluminosilicate i was formed in the exothermic reaction as a primary precipita-~ tion product. After stirrin~ for lO minutes, the suspension i of the precipitation product was either separated as an amor-phous product or transferred to a crystallization vessel where it re~ained for some time at the ele~ated temperature given to crystallize. After draining off the liquor from the crystals i and washing with deionized ~ater uniil the outflowing wash j . water had a pH-value of about 10, the filter residue was dried.
When there is ~ny deviation from this general production pro-cedure, this is mentioned explicitly in the specific part.
~ Thus, for example, in so~e cases for the practical tests, the ; homogenized 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 800-C
In the production of microcrys~alline aluminosili-c~tes, indicated by the suffix "m", the aluminate solution diluted with deionized water was mixed with the silicate solu-t~on and ~ixed in a high-speed intensive stirrer (lO,OOO rp~, "Ultraturra~', made by Janke & Kunkel IK~-Werk, Stauffen/
Breisgau/Federal Republic of Germany), After vigorous stirring -30=

_ , .

~03~55 for 10 minutesJ the suspension of the amorphous precipitation product was trans~erred to a crystallization vessel where the formation of large crystals was prevented by ~tirring the ~uspension. After draining olf the liquor and washing with deionized water until the outflowing water had a pH value of about 10, the fllter residue was dried, then ground in a ball mill and separa~ed in a centrifugal sifter ("Microple ' air ~ifter, made by Alpine, Augsburg, Federal Republic of Germany) into two fractions, of which ~he finer fraction contained no portions ab~ve 10~ m e particle size distribution was de-termined by ~eans of a sedimentation scale . The degree of crystallization ~ an alumin3silica~e can be~determined fro~ the intensity of the interference lines of an X-ray diffraction diagram of the respective product, compared to the corresponding dlagrams of X-ray amorphous or fully crystallized products All data in % are in percent by weight.
The cRlcium binding power OI' the alu~inosilicates or ~orosilicates was determined in the following manner. 1 liter of an aqueous solution, containing 0 5~L~ gm of CaC12 (= 300 ~g CaO/l = 30dH)and adjusted to a pH of 10 with diluted NaOH, was mixed with 1 gm of the alu~inosilicate or boros~licate (on the anhydrous basis, AS). Then the suspension was .stirred vig-orously for 15 minutes at a te~perature ~f 22~C (~ 2C) After filtering off the aluminosilicate, the residual hardness x of the filtrate was determined. From it, the ca'ciu~ binding power was calcul~ted in mg CaO/g~. As according to the for~ula:
(30 - x) . 10 If calciu~ binding power is determined at higher tem-perature, for ex.ample, at 60~C, better values are obtained than ~31=

~3645S
at 22C. Thi~ fact distinguishes th~ aluminosilicates from ~ost of the soluble sequestering agents that have been suggest-ed so far for use in detergents and represents a particular technical progress in their use, Production conditions for aluminosilicate I:
- r ~
Precipitation: 2.985 kg of an aluminate solution o~ the co~position: 17.7~ Na20~ 15.8~ A1203~ 66.6% H20 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 1 Na20. 6.o SiO2, prepared freshly from commercial waterglass and easily alkali-soluble silica Crystallization: 24 hours at 80C
Drying: 24 hours at 100C
Compositlon: 0.9 Na20 . 1 A1203 . 2.05 SiO2 ~. 4,3 H20 (-21,6~ H20) Degree o~ cry8tal-lization: Fully cr~stalline Calcium b$nd$ng power: 150 mg CaO/gm AS, If the product obtained was dri~d for 1 hour at 400C, an aluminum silicate Ia was obtained of the composition:
0,9 Na20 . 1 A1203 , 2.04 SiO2. 2.0 H20 (= 11.~ H20) which is likewise suitable for the purposes of the invention.
Product conditions for aluminosilicate II:
Precipitation: 2.115 kg of an aluminate solution of the composition: 17.7~ Na20 15.8~ A120 66.5~ H20 0,585 kg of sodium hydroxide =32=

~ ~3~5S
9.615 kg Or water 2.685 kg of a 25,8~ sodium silicate ~olution 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 Na20~ 1 A1203. 2.655 SiO2. 5,2 H20 Degree of crystal-lizati~n~ Fully crystal7ine 10 Calcium binding power: 120 mg CaO/gm AS.
This product too can be dehydrated b~ drying (for 1 hour at 400C) to the composition:
0,8 Na20. 1 A1203. 2.65 SiO2, 0.2 H20 Thls dehydration product IIa is likewise suitable for the purposes o~ the invention, The alumino~ilicates I and II show in the ~-ray dif-rraction diagr~m the ~ollowing inter~erence lines, d- values, recorded with Cu-Ka- radiation in A
I II
_ 14,4 12,4 _ 8,8 8,6 : 7,o _

4.
4,1 (~) _ _ 3,8 (+) 3,68 (+) 3,38 (+) ~33=

103~5S
3.26 (~) -2 96 (~) - 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 diffraCtlon diagram, particu-0 larly if the aluminosllicates are not fully crystallized. Fore n~s~
this reason, the d-values which are~et important for the characterization of these types are identi~ied by a "(~
Production conditions for aluminosllicate III
Precipitation: 2 985 kg o~ an aluminate solution o~ the composltion: 17 7~ Na20.~ 15 8~ ~1203~r 66,5~ H20 0,150 kg of sodium hydroxide 9,420 kg of water 2 445 kg o~ a 25,8% sodium silicate solution of the composition: 1 Na20. 6 SiO2 (prepared as in I) Crystallization: none, amphorous precipitate Drying: 24 hours at 25C and 20 torr.
Composition: 0.9 Na20 . 1 A1203 . 2.04 SiO2 47 H20 Degree of crystal-lization: X-ray amorphous Calcium binding power: 160 mg CaO/gm AS
~34=

36~55 Production condition~ for alum$nosilicate IV:
Precipitation: 2.985 kg of an alumlnate solutlon of the composition: 17.7% Na20, 15.8% A1203, 66-5% ~2 0.150 kg of sodium hydroxide 9.420 kg of water 2.445 kg of a 25.8% sodium silicate solu-tlon of the composition: 1 Na20 . 6 SiO2 (prepared as in I) Crystallization: None, amorphous precipitate Drying: 24 hours at 100C, then 1 hour at 400C
Composition: o.g Na20 . 1 A1203 . 2.04 SiO2 . 0.1 H20 Degree of crgstal- -lization: X-ray amorphous Calcium binding power: Due to the extensive drying of the amor-phous precipitate, the calcium binding power was reduced to 20 mg CaO/gm AS: the product was practically unsuitable for the purposes of the invention.
Pr,oductlon con,ditions for aluminosilicate V:
Precipitation: 4.17 kg'of solid aluminate of the composi-tion 38% Na20, 62% A1203 10.83 kg of a 34.9% sodium silicate solu-tion of the composition: 1 Na20 . 3.46 SiO2 Crystsllization: None, amorphous precipitate Drying: 24 hours at 100C
Composition: 1.5 Na20 . 1 A1203 . 2 SiO2 3 H20 .

db/~ 35 .~ , , , - ~r Degree of crystaL- 1036~55 lization: X-ray amorphous Calcium binding power: 140 mg CaO/gm AS
Production _nditions for aluminosilicate VI:_ _ Precipitation: 8.37 kg of an aluminate solution of the composition: 20.0~ Na20, 10.2~ A1203, 69.8~ H20 0,09 kg of sodium hydroxide

5,34 kg of water 1,20 kg of microcrystalline sil~ca (Aero~il) Crystallization: None, amorphous precipitate Drying: 24 hours at 100C
Composition: 0.9 Na20 , 1 A1203 , 2.04 SiO2 , 6,7 H20 Degree of crystal-lization: X-ray amorphous Calclum binding power: 145 mg CaO/gm AS
Production condition~ for aluminosilicate VII: 0 Precipitation: 3,255 kg of an aluminate solution of the composition: 17,7% Na20, 15,8~ A12G3, 66.5~ H20 o,o6 kg of sodium hydroxide 9.465 kg of water 2.22 kg of a 34.9% sodium silica.te solution of the composition: 1 Na20 . 3.46 SiO2 Crystallization: None, amorphous precipitate Drying: 24 hours at 100C
Composition: 1 Na20 . 1 A1203 . 2 SiO2 . 1 H20 (=6% H20) =3~= ~

~36~55 Degree of crystal-lization: X-ray amorphous Calcium binding power: 150 mg CaO/gm AS
Production conditions for aluminosilicate VIII:
Precipitation: 2,115 kg of an aluminate solution of the composition: 17.7% Na20, 15.8~ A1203, 66.5~ H20 0.585 kg of sodium hydroxide 9.615 kg of water 2.685 of a 25.8% sodium silicate solution of the composition: 1 Na20 . 6 SiO2 Crystallization: None, amorphous precipitate Drying: 24 hours at 100C
Co~po~ition: 0.8 Na20 . 1 A1203 . 2,65 SiO2 . 4 H20 D~gree of crystal-lization: X~ray amorphous C~lclum blndln~
powcr: 60 mg CaO/gm AS
20 Production condltions ~or aluminosllicate IX:
Precipitation: 3,41 kg of an aluminate solution of the composition: 21,4~ Na20, 15,4% A1203, 63.2% H20 10,46 kg of water 1,13 kg of a 34.9~ sodium silicate solution of the composition: 1 Na20 . 3.46 SiO2 Crystallization: None~ amorphous precipitate Drying: 24 hours at 100C
Compasition: 1 Na2 1 A1203 . 1 SiO2 . 1. 4 H20 =37=

J~Q364~S
Degree of c,r~sta~,-lization: X-ray a.morphous Calcium binding power: 120 ~g CaO/gm AS
Production conditions for aluminosilicate X:
Precipitation: 2.835 kg of an aluminate solution of the composition: 14.2% Na20, 17.2~ A1203, 68.6~ H20

6.93 kg of' water 5.235 kg of a 34.9~ sodium silicate solution of the composition: 1 Na20 . 3.46 SiO2 Crystallization: None, amorphous precipitate Drying: 24 hours at 100C
Compo~ition: 1 Na20 , 1 A1203 . 5 SiO2 . 2.8 H20 Degree of crystal-lization: X-ray amorphous Calclum binding power: ' 100 mg CaO/gm AS
Prod _ _ ~ for aluminosilicate XI:
Precipitakion: 2.86 kg of an aluminate solution of` the composition: 13.8~ Na20, 16.7% A1203, 69.5~ H20 6.01 kg of water 6.13 kg o~ a 34.9~ sodium silicate solution of' the composition: 1 Na20 . 3.46 SiO2 Crystallization: None, amorphous precipitate Drying: 24 hours at 100C
Composition: About 1 Na20 . 1 A1203 . 6 SiO2 . 3.2 H20 ,38~

64~5 Degree of crystal-lization: X-ray amorphous Calcium binding power: 60 ~g CaO/gm AS
Production conditions for aluminosilieate XII:
Precipitation: 2~01 kg o~ an aluminate solution of the composition: 20.0~ Na20, 10.2~ A1203, 69.8% H20 1.395 kg of sodium hydroxide 9.045 kg o~ water 2.19 kg o~ a 25.8~ sodium silicate solution of the composition: 1 Na20 . 6 SiO2 (prepared as under I) Crystallization: 24 hours at 80C
Drying: 24 hours at 100C
Compo~ltion: 0.9 Na20 . 1 A1203 , 2 SiO2 . 3 H20 Degree of crystal-llæa-tion: Fully crystalline Calcium bindln~
powcr: 160 mg CaO/gm AS
Production conditlon8 ~`or aluminosilicate XIII:
Prccipitatlon: 2,985 kg of an alu~inate solution of the co~posltion: 17.7% Nfl20, 15.8% A1203, ~6,5~ H20 0,150 kg of sodium hydroxide 9,520 kg of water 2,445 kg of a 25,8~ sodium silicate solution of the co~position: 1 Na20 . 6 SiO2 (pre-pared as in I) Crystallization: 24 hours at 80C

~39=

~3~SS
For the productlon of a potassium aluminosilicate, the liquor waR drained off, the residue washed with water and sus-pended in an aqueous KCl solution. After heating for 30 minutes to 80-90C, the product was filtered off and washed.
Drying: 24 hours at 100C
Composition: 0.28 Na20 . 0.62 K2O . 1 A1203 . 2-04 SiO2.
4.3 H2O
Degree of crystal-lization: Fully crystalline Calcium binding power: 170 mg CaO/gm AS
Production conditions for aluminosilicate XIV:
Precipitation: 8.450 kg of an aluminate solution of the composition: 11.3% Na20, lS.7% A12O3, 70'0% ~2 6.550 k8 of a 34.9% sodium silicate solution of the composition: 1 Na2O . 3.46% SiO2 Crystallization: None, amorphous precipitate Drying: None Co~position: 1.5 Na20. 1 A1203 . 2 SiO2 . x H20 De8ree of crystal-lization: X-rsy amorphous Calcium binding power: 120 m8 CaO/gm AS
Production conditions for aluminosilicate XV:
Precipitation: As for aluminosilicate XIV
Crystallization: 24 hours at 80C
Drying: None Composition: 1.5 Na20 . 1 A12O3 . 2 SiO2 2 db/~.~P~ -40-Degree of cryRtal-~1~36~5 lization: Fully crystalline Calcium binding power: 170 mg CaO/gm AS
Production conditions for borosilicate XVI:
Precipitation: 3.20 kg of a borate solution of the compo-~ition: 19.7% Na20, 19.7% B2O3, 60.6% H20 9.55 kg of water 2.55 kg of a 34.5% sodium silicate solu-tion of the composition: 1 Na20 . 3.46 SiO2 Crystallization: 24 hours at 80C
Drying: 24 hours at 100C and 20 torr.
Composition: 1.5 Na2O . 1 B2O3 . 2 SiO2 . 1.5 H2O
Degree of crystal-lization: Primarily crystalline Calcium binding power: 120 mg CaO/gm AS
The pr~mary particle sizes of the aluminum or boron ~llicates I - XVI described here range from 10 to 45 m~.
P.roduction contltions for aluminosilicate Im:
Precipitntion: As in aluminosilicate I
C~y~tallization: 6 hours at 90C
Drying: 24 hours at 100C
Compo~ition: 0.9 Na20 . 1 A1203 . 2.05 Si02 . 4.3 H20 ~- 21.6% H2O) Degree of crystal-lization: Fully crystalline Calcium bindin8 power: 170 mg CaO/gm AS

db/~ 41-.
-~36~55 Production conditions for aluminosilicate IIm:
Precipitation: As for aluminosilicate II
Crystallization: 12 hours at 90C
Drying: 24 hours at 100C and 20 torr.
Composition: 0.8 Na20 . 1 A1203 , 2,655 SiO2 5-2 H20 Degree of cr~stal-lization: Fully crystalline Calcium binding power: 145 mg CaO/gm AS
Production conditions for aluminosilicate XIIm:
Precipitation: As for aluminosilicate XII
Crystallization: 6 hours at 90C
Composition: 0.9 Na20 . 1 A1203 . 2 SiO2 . 3 H20 Degree of crystal-lization: Fully crystalline Calcium blnding power: 175 mg CaO/gm AS
Production conditions for aluminosilicate XIIIm:
Prccipitation: As for aluminosilicate XIII
Cr~stalli~ation: 6 hours at 90C
For the production of the potassium-aluminum silicate the llquor was drained off, the residue was washed with water and suspended in an aqueous KCl solution. The product was filtered off after heating for 30 minutes to 80-90C and washed.
Drying: 24 hours at 100C
Composition: 0.28 Na20 , 0.62 K20 . 1 A1203 . 2.04 SiO2 .
4.3 H20 Degree of crystal-lization: Fully crystalline Calcium binding power: 180 mg CaO/gm AS

=42=

1~36~55 Production conditions for aluminosilicate XVm:
Precipitation: As for aluminosilicate XIV
Crystallization: 24 hours at 80C
Drying: The filter cake was not dried but suspended in water after washing and used in this form for the application tests.
Composition: -9 Na20 1 A1203 . 2 SiO2 . x H20 Degree of crystal-lization: Fully crystalline Calcium binding power: 170 mg CaO/gm AS
Production conditions for aluminosilicate XVIIIm:_ Precipitation: As for aluminosilicate XIV
CrystallizRtion: 6 hours at 90C
Drying: 24 hours at 100C
Composition: 0,9 Na20 . 1 A1203 , 2 SiO2 . 4.4 H20 Dcgree of crystal-liz~tion: Fully crystalline Calcium binding power: 172 mg CaO/gm AS
Production conditions for aluminosilicate XIXm:_ Precipitation: 2,96 kg of an aluminate Rolution of the composition: 17.7~ Na20, 15.8~ A1203, 66~ H20 0.51 kg of sodium hydroxide 8.45 kg of water 3.00 kg of a commercial sodium silicate solution of the composition: 8.0% Na20, 26.9~ SiO2, 65-1~ H20 Crystallization: 12 hours at 90C

=43=

103~455 Drylng: 12 hours at 100C
Composit~on: 0.93 Na20 . 1 Al203 . 2.75 SiO2 . 5~5 H2O
Degree of crystal-lization: Fully crystalline Calcium binding power: 12-5 mg CaO/gm AS
Production conditions for aluminosilicate XXm:
Precipitation: 0.76 kg of an aluminate of the composition:
36.0% Na20, 59.0% Al203, 5.0% H2O
0.94 kg of sodium hydro~ide 9.49 kg of water 3.94 kg of a commercial sodium silicate solu-tion of the composition: 8.0% Na20, 26.9% A 2 3~ 2 Crystallization: 12 hours at 90C
Drying: 12 hour~ at 100C
Composition: 0~9 Na20 1 Al23 3-1 SiO2 ~ 5 H2O
Degree of crystal-lization: Fully crystalline Calcium binding power: 110 m8 CaO/gm AS
The particle size of the above described microcrystal-line products Im - XIIIm and XVIIm - XXm, determined by sedimen-tation snalysis, wa9 in the following range:
> 40 ~ = 0% maximum range of the particle size ~ 10 ~ - 100% distribution curve at 3 - 6 < 8 ~ ~ 50 - g5~
The particle size distribution of the product XVm was in the following range:

db/~l~ ~44~

1~3~i9L5S
- > 40~ ~ 0% maximum range of the partlcle size < 10~ ~ 100~ distribution curve at 1 - 3 < 8~ ~ 99~
The salt constituent~ contained in the detergents of the examples, such as surfactants in salt form, other organic salts, as well as inorganic salts, were present as sodium salt, unless explicitly stated otherwise. This also applies to the precipi-tation inhibitors or chelating agents which are designated 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, preferably 11 to 13 carbon atoms in the alkyl chain, ob-tained by condensation of straight-chain olefins with benzene and sulfonation of the alkylbenzene thus obtained.
"HPK-sulPonate" a sulfonate obtained from the methyl ester of hydrogenated palm kernel fatty aeids by sulfonation with SO3-OA ~ x EO OR "TA ~ x EO" the addition products ofethylene oxide ~EO) to technical oleyl aleohol (OA) or to tallow ~atty alcohol ~TA) ~iodine number ~ 0.5), where the values for x lndieate the molar amount of ethylene oxide added to 1 mol of alcohol.
"NTA" and "EDTA" the salts of nitrilotriaeetie aeid and ethylenediaminetetraaeetic acid.
"~EDP" the salt of l-hydroxyethane-l,l-diphosphonie acid.
"DNDP" the salt of dimethylaminomethane-diphosphonie acid.
~ CNC" the salt of carboxymethylcellulose db/~ ~ ~45~

1~36455 The wa~hing effects achieved with the aluminosllicates according to the invention were demonstrated in washing tests on sample fabrics of unflnished and wash-and-wear (crease-resistant) cotton and on blended fab~ics of polyester and finished cotton, with a test soiling of soot, iron oxide, kaolin and skin fat (test fabrlcs produced by Waschereilforschungsinstitu~ Krefeld).
The tests were carried out with tap water of 16 dH
partly in the "Launder-0-Meter'~ and partly in a commercial 4 kg drum washing machine (25 liter liquor capacity). ~n the "Launder-0-Meter" each vesse] was loaded with 2 test fabrics each of 2.1 gm and with unsoiled rags of the same material, likewise weighing each 2.1 gm. The drum washing machine was loaded with 6 test fabrics each of 20 x 20 cm and 3.8 kg of unsoiled fabrics of the same type.
The aluminosilicate concentration of the wash liquor, ~ust as the aluminosilicate contents of detergent formulas, relates to the anhydrous component of the product (determined by dehydration or 1 hour at 800C). This applies both to the use of suspensions oE the X-ray-amorphous precipitation product and ~0 for the crystals.
The washing times indicated in the various tests refer to thc duration of the treatment at the indicated temperature, including the heating times. Cold tap water was used for rins in8-After the fabric samples were washed in the "Launder-0-Meter", they were rinsed 4 times with tap water for 30 minutes each. In the tests made in a commercial washing machine, the se~uence of the wa~hing and rinsing cycles was determined by the autoDatic washing program, as it was provided for the db/ P ~ -46-~ 36455 respective fabric material. After drying and lroning the f~brics, their remission values were measured in a photoelectric photometer "Elrepho" by Zeiss under filter 6 (permeability ~ax-imum at 461 mm). The test fabrics used in the tests had a remission value of about 43 when they were received.

_ _ . . .
This example de~onstrates the washing action of various alu~inosilicates to be used according to the invention without the addition of other de~ergent ingredients. 0 Working conditions:
unfinished cotton, 10 gm/l aluminosilicate liquor ratio 1:12, washed for 30 minutes at 90C in the "Launder-O-Meter"
In parallel tests, the removal o~ dirt was determined with water without any further addition and with the addition o~ 10 gm/l o~ tripolyphosphate The water and tripolyphosphate, values thus ~ound, as well as the other valuas,are given in the ~ollowing Tablc I:

Addltion Remission No addltion 42.4 NasP30lo 76 8 Aluminosilicate I 68 0 Aluminosilicate II 66 0 Aluminosilicate III 67.5 Aluminosilicate IV 50.5 Aluminosilicate VIII 62.0 Alu~inosilicate XIII 69,3 ,47=

~L0364SS
TABLE I l ontinued) Addition _ Remission Aluminosilicate XIV ~) 66.o Aluminosilicate XV ~) 69.4 Borosilicate XVI 66.o +) These alumino~ilicates were, as a precipitate or crystals, used after decanting the supernatant aqueous solution without drying. _ _ In order to demonstrate the i~provement of the wash-ing action of an aluminosilicate con~aining detergent, deter-gents o~ the following co~position were utilized. They were produced by mixing the dry aluminosilicate with the perborate, a precipitation inhibitor, and a detergent powder obtained by heat-atomizatlon whlch did not contain the three above-mentioned components, and by adding the sequestering agents or precipi-tatlng agents:
5.3~ ABS
2,0~ TA ~ 14 E0 2,8~ BaP al~-22 ~atty acids 0 or 4,2~ sequestering or precipitating agent for calcium ~5,0% alumlnosilicate Ia 22.5~ .perbor~te 2,5% Na20 . 3.3 SiO2 1.2~ CMC
1.7~ MgSiO3 2.1% Na2S0 11. lqb H20 Working conditions:
finished cotton, 9 gm/l detergent liquor ratio 1:12, washed for 30 minutes at 90C in the "Launder-0-Meter".
The results are given in Table II.
=48=

.

~,~36~SS
TABLE II
Sequestering or precipitating agents for calcium (as Na-salts) Remission No addition, replaced by Na2S04 64.o Oxalic acid 68.0 Tartaric acid 66.o Citric acid 68.5 O-carboxymethyl-tartronic acid 7~.8 O-carboxymethyl-methyltartronic acid 75.~
NasP3010 71.0 Alanine 68,9 Glutamic acid 72.0 Nitrilotriacetic acid 71.0 Ethylenediaminetetraacetic acid 67.5 N,N-dimethylamino-methanediphosphonie acid 71.0 Polyacrylic acid 69.5 Polyhydroxy-polycarboxyllc acid I +) 71.7 Polyhydroxy-polyearboxylie aeid II -~) 72.0 ~) These two substances were produced by polymerization of aerolein and treatment o~ the polymer according to C3nnizzaro ln the presence of ~ormaldehyde.

With a detergent of the above-described formula, where both the sequestering or precipitating agent for calcium and the aluminosilicate are replaced cQmpletely by sodium tripolyphosphate, a remiseion value of 72.5 was obtained under the above washing conditions.

=49=

~36455 This example demonstrates the e~fect of the step-wise replacement of the triphosphate contained in a detergent by aluminosilicate The composition o~ the detergents was within the ~ollowing recipe:
5.3~ ABS
2.0~ TA + 14 EO
2.8~ soap C12_22 fatty acids 4.2% to 33.4~ NasP310 45% to 0.0~0 alu~lnosilicate Ia 22.1% NaB02 . H22 3 H20 2.5~ Na20 3.3 SiO2 1.2% CMC
1,7~ MgSiO3 2.1~ Na2SO,~
Balance H20 Test cor.dlt~on~:
fin!l~hed cotton, 9 gm/l detergent liquor ratlo 1:12, wa~hed ~or 30 minutes at 90C in the "Launder-O-Meter"
m e wa~hing results are given in Table III.

=5o=

~L~3645i5 TAB~E III

% content o~ NasP3010 % content o~ alumino-in detergent silicate in deter~ Remission (%) 4.2 ~5. 72 8.3 39.4 72 12.5 33.8 73 16.7 28.1 73 20.8 22.5 73 25.0 16.9 73 29.2 11,3 73 33.~ 0 72 EXAMPLES 4 and 5 These examples demonstrate the washing action of two detergent~ according to the invention on textiles, compared to detergents in which the aluminosilicate is replaced b~
N~5P3010, The detergents had the following composition, "e"
indicating the detergent according to the invention, and "v"
thc re~erence d~tergent.
Component o~ de- ~ by wei~ht of component in the detergent tergent l~ Lre ~
ABS ~,0 8,0 - -TA -t 14 EO 3,0 3,0 - -OA ~ 10 EO - - 15,0 15 0 Soap Clg_22 Fatty acids 3,5 3,5 3 0 3 0 Aluminosilicate Ia - 45.0 - 27 0 NasP3010 33 4 2 5 10.0 3 0 NaB2 H22 3 H20 22 1 22.1 24 0 24 0 Na20 . 3.3 SiO2 2.5 2.5 10.0 10 0 CMC 1.2 1,2 - -MgSiO3 1.7 1.7 Na2S4 19 0 2 1 30 0 10,0 H20 5 6 8 4 8,0 8.0 =51=

~936~55 Washing conditions: native and finished cotton, cotton poly-ester blend detergents 4v and 4e: 9 gm/l 5v and 5e: 7.5 gm/l Liquor ratio: 1:5 Drum washing machine with washing program ~or boiling wash, maximum temperature, 9~C. The washing results are given in Table IV.
TABIE. TV
10 Detergent Remission of washed fFbttc in~
according Native nis ed o o to example cotton Cotton _ ~ blend 4v 83 74 70 4e 82 73 74 5v 82 74 74 5e 82 73 74 In order to obtain the same washing results a~ with tripolyphosp~te, it ls advisable to select a alum~nosilicate concentration ~llghtly higher than the tripolyphosphate con-centr~tions of the reference liquors.

Detergent~ of the following formulas 6a and 6b are aultable for use in commerclal laundries:
=52=

1~364S5 Component Content in_~ n the detergent ABS 1.4 1.4 OA + 10 EO 7.6 7.6 Na2C3 `18.3 18.3 Na2SiO3 5.4 5.4 Aluminosilicate V18.3 33.4 Na5P3010 16.7 5.8 CMC 0.8 0,8 Brightener, Na2S0410.0 10.0 H20 21.5 17.3 The NasP301o can be replacad in detergent 6a by a phosphorus-free organic sequestering agent for calcium; in detergent 6b by HEDP or any other calcium-sequestering phos-phonate~ or by a phosphorus -free sequest~ring agent for calcium, or by a non-sequestering calcium precipitating agent (e.g, oxalic acid, adipic acld or sebacic acid in the form of their water-solublc sal~s), Using each o~ ~hese detereents, normally soiled hou~ehold l~undry was wa~hed under thc following condltions:
Type of m~chine: Centrifugal washing machine of 90 kg capacity, loaded with 75 kg wash.
Water: Tap water softened to 5 dH.
1, 1st washing cycle: 25 gm detergent/kg dry wash, iquor ratio 1:4, 9 minutes at 60C.
2, 2nd washing cycle: 20 gm detergent/kg dry wash, 0,5 gm activated oxygen (as (H202) /kg dry wash, liquor ratio 1:4, 12 minutes at 90C.
3. rinsing cycles: 2 x with softened, 2 x with unsoftened water.
In both cases the washing result was completely satisfactory.

-53=

~364S5 A detergent suitable for washing greatly soiled work clothes has the following composition:
18.0~ OA + 10 EO
60.0% Na2C03 12.0% aluminosilicate V
5.5% O-carbo~ymethyl-tatronic acid (Na-salt) 1.3% CMC
0.3~ brightener 2.9~ H20 ~ leaching wa~hing assistant~, of which product 8a is suitable as an additive to wash liquors containing surface-active agents in commercial làundries, and product 8~ is suitable a8 a cold-power additive for the rinsing water, have the ~ollowin~ composltion:
by weight of component in the de-tergent according to example Com~onent ~a ~D
Na2B02. H22 3 H20 36 o 18.0 ~ctraacctgl-~lycoluril ~ la.O
MgS103 3.6 3.6 A~umlnosilicate V 31.5 31.5 Na citrate 7.2 7.2 Na2C3 15.0 15.0 Brightener 0.3 0 3 H20 6.4 6.4 The following are the formulas of a few additional aluminosil~cate-containing detergents.
=54=

~)3~455 % b~ weight of component in the de-tergent accordin~ to example Detergent component y lU i i~
TA + 14 EO 7.0 10,310,7 6,8 Aluminosilicate VII 52,1 47.251.2 64.2 Na5P3~10 __ 5.1 3.2 6,2 Sodium citrate 7.3 -- 2.1 --EDTA 0,2 0.2 0,1 0.3 Na20 . 3.3 SiO2 1.7 6.3 3.1 3.5 NaB02. H22 3 H20 2~.9 24.9 20.3 --CMC 0.8 1.6 1.1 2.0 Na2S0 4 + H20 6.o 4.4 8.2 17.0 by weight ~ component in the de-ter~ent according to example Detergent co~ponent 13 I4 1~ 1~
HPK-sul~onate 1,0 2,6 -- 1,6 ABS 4.5 4~7 7.1 __ TA ~ 14 EO 2,3 1,9 -- 6.4 OA ~ 10 EO -- -- -- 4,1 Soap 2,0 1.6 3.2 --Alumino~ilicatc VII 45,0 47,3 48,1 49.3 Na5P3010 5~ 6.3 a.o 7,2 E~TA 0,2 0.9 0,2 0,2 Na20 , 3.3 SiO2 6,5 3.7 2,6 3,4 NaB02 ~ H22 ~ 3 H20 25,1 26.3 22,3 22,1 CMC 1.3 '9 1,5 1.6 Na2S04 + H20 7.1 3.8 7.0 4.1 =55=

~al36455 As it can be seen from the examples, particularl~
from the tests described thereln, the aluminosilicates with cation-exchanging capacity to be used according to the inven-tion are capable of improving the washing power of a detergent by binding the calcium contained in the water and in the dirt and to replace tripolyphosphate part}y or completely As far as the detergeni for~ulas still contain tripolyphosphate, the latter can be replaced, îf necessary, by phosphorus-free se-questering agents. Suitable sequestering agents are found among the compounds of Table II in Example 2~oxælic acid is not a sequestering agent, but a precipitating agent).
Though the alu~inosilicates are insoluble in water, they can be washed out easily ~rom the washed fabrics, and there are no deposits either in the washing machine or in the eewer pipes.
The tests and detergents described in Examples 1 to 16 were al~o carried out or produced respectively by using the microcrystalline aluminosllicates. A better action of the mlcrocrystalline aluminosillcates waa found at least when the products to bc compared have the same composition, Specifically th~ ~ollowing microcrystalllne aluminosilicates were used for the productlon of deter~enta or used in the washing tests In Example 1: The aluminosilicates Im, IIm and IVm In Example 2: The aluminosilicates XIIm In Example 3: The alumino~ilicates Im In Example 4: The aluminosilicates XIIIm in Example 5: The Aluminosilicates xIIIm =56=

1~369~5 n Example 6: The aluminosilicate XVIIIm. The Na5P3010 could be replaced in detergent 6a by a pho~phorus-free organic sequestering agent for calcium;
in detergent 6b by HEDP or any other calcium-sequestering phosphate, b~ a phosphorus-free sequestering agent for calcium, or by a non-sequestering calcium precipitant (e.g, oxalic acid, adipic acid or sebacic acid in the form of their water-soluble salts).
In~Example 7: The aluminosilicate IIm In Example 8: The aluminosilicate Im In Exam-ples 9 to 12: The aluminosilicate XII
In Exam~les 1~ to 16: The aluminosilicate XVIIIm Detergents of the following composition were also produced by U8i~g the aluminosilicates XIIm and XVIIIm, -57=

% by weight of component in the de-ter~ent according to example _ Deter~ent component _17 1~ ly ~
TA ~- 14 EO 7.0 10.3 10.7 6.8 Aluminosilicate XIXm50.1 45.2 49.2 62.2 NasP3010 5,1 3.2 6.2 Sodium citrate 7.3 -- 2.1 --EDTA 0.2 0,2 0.1 0.3 Na20 . 3.3 SiO2 1.7 6,3 3.1 3.5 NaB02 . H22 3 H20 24.9 24.9 20.3 --CMC 0.8 1.6 1,1 2,0 Na2S04 + H20 8.0 6.4 10.2 19,0 ~ b~ weight of component in the de-Detergent component tergent accordin~ to example _ HPK- sulfonate 1.0 2.6 -- 1.6 ABS 4-5 4~7 7.1 __ TA ~ 14 EO 2.3 1.9 -- 6,4 OA ~ 10 EO -- -- -- 4,1 ~oap 2,0 1.6 3,2 --Aluminosillcatq XXm43,0 45,3 46,1 45,3 Na5P3010 5.0 6,3 8,0 7.2 E~TA 0.2 0.9 0.2 0.2 Na20 . 3.3 SiO2 6~5 3.7 2.6 3.4 NaB02 . H22 3 H2025.1 26.3 22,3 22,1 CMC 1.3 0.9 1.5 1.6 Na2S4 ~ H20 9.1 5.8 9,0 8,1 The microcrystalline aluminosilicates according to the invention can be washed out better, particularly in edges and corners o~ blanket covers and pillow cases, as well as on collars and cuffs of shirts, =58=

~L~3ti9~S5 The preceding specific embodiments are illustrative of the practice of the invention It is to be understood, however, that other expedients known to those skilled in the art or disclosed herein may be employed without departing from the spirit of the invention or the sco~e of the append-ed claims.

-59=

Claims (28)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In the process of washing soiled textiles by contacting soiled textiles with an aqueous solution contain-ing a water softening agent for a time sufficient to disperse or dissolve the soil from said soiled textiles into said aqueous solution, separating said aqueous solution and recovering said textiles substantially soil-free, the improve-ment which consists of using a finely-dispersed water-insoluble silicate compound containing some combined water and having primary particles in the size range of from 100 µ to 0.1 µ
and 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 and potassium, x is a number 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, as said water softening agent.
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 3 wherein said crystalline silicate compounds have, in the X-ray diffraction diagram, the following d-values in Angstrom units:
12.4 8.6 7.0 4.1 3.68 3.38 3.26 2.96 2.73 2.60
5. The process of Claim 3 wherein said crystalline silicate compounds have, in the x-ray diffraction diagram, the following d-values in Angstrom units:
14.4 8.8 4.4 3.8 2.88 2.79 2.66
6. The process of Claim 1 wherein at least 80% by weight of the particles of said silicate compound have a size of from 10 µ to 0.01 µ.
7. The process of Claim 6 wherein at least 80% by weight of the particles of said silicate compound have a size of from 8 µ to 0.1 µ.
8. The process of Claim 1 wherein said silicate compound has no primary or secondary particles above 40 µ.
9. The process of Claim 1 wherein said silicate compound is employed in an amount whereby the residual hard-ness of said aqueous solution is from 0.5° to 3° dH.
10. The process of Claim 1 wherein said aqueous solution contains from 0.5 to 2 gm/liter of at least one other compound capable of sequestering calcium or inhibiting the precipitation of calcium carbonate.
11. The process of Claim 10 wherein said other compound is water-soluble.
12. The process of Claim 11 wherein said one other water-soluble compound capable of sequestering calcium or inhibiting the precipitation of calcium carbonate is a compound selected from the group consisting of alkali metal metaphosphates, alkali metal polyphosphates and alkali metal salts of organic acids selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers of polyhydric compounds and poly-anionic polymeric carboxylic acids and phosphonic acids.
13. Washing auxiliary compositions consisting essentially of (a) from 5% to 95% by weight of a compound capable of sequestering calcium or inhibiting the precipitation of calcium carbonate selected from the group consisting of organic salts and inorganic salts, and (b) from 95% to 5% by weight of a finely-dispersed water-insoluble silicate compound containing some combined water and having primary particles in the size range of from 100 µ to 0.1 µ and a calcium binding power of 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 and potassium, x is a number 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.
14. The washing auxiliary compositions of Claim 13 wherein component (b) is present in an amount of from 15% to 60% by weight.
15. The washing auxiliary compositions of Claim 13 wherein said component (a) is water-soluble.
16. The washing auxiliary compositions of Claim 15 wherein said water-soluble component (a), a compound capable of sequestering calcium or inhibiting the precipita-tion of calcium carbonate, is a compound selected from the group consisting of alkali metal metaphosphates, alkali metal polyphosphates and alkali metal salts of organic acids selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers of polyhydric compounds and polyanionic polymeric carboxylic acids and phosphonic acids.
17. Washing, rinsing and cleansing compositions consisting essentially of (a) from 5% to 95% by weight of a compound having a cleaning action selected from the group consisting of (1) anionic surface-active compounds, nonionic surface-active compounds, amphoteric surface-active com-pounds, and mixtures thereof, (2) organic builder salts and inorganic builder salts, and (3) mixtures of (1) and (2), and (b) from 95% to 5% by weight of a finely-dispersed, water-insoluble silicate compound containing some combined water and having primary particles in the size range of from 100 µ to 0.1 µ and a calcium binding power of 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 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.
18. The washing, rinsing and cleansing composi-tions of Claim 17 wherein said component (b) is present in an amount of from 15% to 60% by weight, and said component (a) is from 2% to 40% by weight of a surface-active compound selected from the group consisting of anionic surface-active compounds, nonionic surface-active compounds, amphoteric surface-active compounds, and mixtures thereof, and from 2% to 15% by weight of a water-soluble compound capable of sequestering calcium or inhibiting the precipitation of calcium carbonate selected from the group consisting of organic salts and inorganic salts.
19. The washing, rinsing and cleansing composi-tions of Claim 18 containing in said component (a) a further amount of from 5% to 60% by weight of inorganic non-seques-tering builder salts.
20. A bleaching, washing, rinsing and cleansing composition consisting essentially of from 10% to 40% by weight of an activated oxygen bleaching compound and from 60% to 90% by weight of the washing, rinsing and cleansing composition of Claim 17.
21. The process of Claim 1 conducted in an absence of water-soluble phosphorus-containing compounds.
22. The process of Claim 1 wherein said aqueous solution contains less than 1.5 gm per liter of water-soluble phosphates.
23. The process of Claim 22 wherein said aqueous solution contains from 0.1 to 1 gm/liter of water-soluble phosphates.
24. The washing auxiliary compositions of Claim 13 wherein said silicate compound is crystalline.
25. The washing, rinsing and cleansing compositions of Claim 17 wherein said silicate compound is crystalline.
26. In the process of washing soiled textiles by contacting soiled textiles with an aqueous solution containing a water softening agent for a time sufficient to disperse or dissolve the soil from said soiled textiles into said aqueous solution, separating said aqueous solution and recovering said textiles substantially soil-free, the improvement which con-sists of using a mixture consisting essentially of (a) from 5% to 95% by weight of a compound capable of seques-tering calcium or inhibiting the precipitation of calcium carbonate selected from the group consisting of water-soluble organic salts and water-soluble inorganic salts, and (b) from 95% to 5% by weight of a finely-dispersed, water-insoluble, crystalline silicate compound containing some combined water and having primary particles in the size range of from 100 µ to 0.1 µ and a calcium binding power of 100 to 200 mg CaO/gm of anhydrous active substance and the formula on the anhydrous basis (Na2O)x ? Me2O3 ? (SiO2)y where x is a number 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, as said water softening agent.
27. Powdery washing, rinsing and cleansing compo-sitions consisting essentially of (a) from 50% to 95% by weight of a compound having a cleaning action selected from the group consisting of (1) anionic surface-active compounds, nonionic surface-active compounds, amphoteric surface-active com-pounds, and mixtures thereof, (2) organic builder salts and inorganic builder salts, and (3) mixtures of (1) and (2), and (b) from 50% to 5% by weight of a finely-dispersed, water-insoluble, crystalline silicate compound containing some combined water and having primary particles in the size range of from 100 µ to 0.1 µ and a calcium binding power of 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 and potassium, x is a number 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.
28. The powdery washing, rinsing and cleansing compositions of Claim 27 wherein M is sodium.
CA 197628 1973-04-13 1974-04-16 Washing compositions containing inorganic silicates and method of washing textiles Expired CA1036455A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT327773A AT368185B (en) 1973-04-13 1973-04-13 A process for washing and bleaching fabrics, as well as means for performing the method
AT800173A AT396691B (en) 1973-09-17 1973-09-17 Textile cleaning bath contg alumino silicates - as fine dispersion functioning as calcium sequestering agents
AT944973A AT375391B (en) 1973-11-09 1973-11-09 A method for washing and bleaching of textiles and medium to

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CA1036455A true CA1036455A (en) 1978-08-15

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JP (3) JPS5761798B2 (en)
CA (1) CA1036455A (en)
DK (1) DK151231C (en)
ES (1) ES425203A1 (en)
FI (1) FI58652C (en)

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EP0273377A2 (en) * 1986-12-31 1988-07-06 Henkel Kommanditgesellschaft auf Aktien Phosphate-free detergent with a reduced foaming tendency
US5972668A (en) * 1994-06-28 1999-10-26 Henkel Kommanditgesellschaft Auf Aktien Production of multi-enzyme granules
US6140401A (en) * 1994-07-27 2000-10-31 Henkel Kommanditgesellschaft Auf Aktien Use of a stabilizer combination in the production of films of polyvinyl chloride by the calendering process
US5892027A (en) * 1995-03-07 1999-04-06 Henkel Kommanditgesellschaft Auf Aktien Process for the production of neutralized polysaccharide-based polycarboxylates
US5856470A (en) * 1995-03-22 1999-01-05 Henkel Kommanditgesellschaft Auf Aktien Oxidation process for producing polycarboxylates from polysaccharides
US5904736A (en) * 1995-04-28 1999-05-18 Henkel Kommanditgesellschaft Auf Aktien Cellulase-containing washing agents
US6187739B1 (en) 1995-09-21 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Paste-form washing and cleaning agents
US6409770B1 (en) 1995-12-08 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Bleaching and washing agents with enzyme bleaching system
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
US6153576A (en) * 1996-02-16 2000-11-28 Henkel Kommanditgesellschaft Auf Aktien Transition-metal complexes used as activators for peroxy compounds
US6235695B1 (en) 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6075001A (en) * 1996-04-26 2000-06-13 Henkel Kommanditgesellschaft Aug Aktien Enol esters as bleach activators for detergents and cleaners
US6248708B1 (en) 1996-09-05 2001-06-19 Henkel-Ecolab Gmbh & Co. Ohg Paste-form detergent containing a mixture of ethoxylated alcohols
US6329333B1 (en) 1997-01-30 2001-12-11 Henkel-Ecolab Gmbh & Co. Ohg Pastelike detergent and cleaning agent
US6417151B1 (en) 1997-04-04 2002-07-09 Henkel Kommanditgesellschaft Auf Aktien Activators for peroxide compounds in detergents and cleaning agents
US6703357B1 (en) 1997-07-30 2004-03-09 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent for hard surfaces, containing glucanase
US6417152B1 (en) 1997-07-30 2002-07-09 Henkel Kommanditgesellshaft Auf Aktien Detergent containing glucanase
US6541233B1 (en) 1997-07-30 2003-04-01 Henkel Kommanditgesellschaft Auf Aktien β-glucanase from a bacillus
US6380147B1 (en) 1998-06-03 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Detergents containing amylase and protease
US6391838B1 (en) 1999-03-31 2002-05-21 Henkel Kommanditgesellschaft Auf Aktien Detergents containing enzymes and bleach activators

Also Published As

Publication number Publication date Type
DK151231B (en) 1987-11-16 grant
JPS549A (en) 1979-01-05 application
ES425203A1 (en) 1976-11-01 application
FI58652C (en) 1983-05-09 grant
JPS5761798B2 (en) 1982-12-25 grant
JPS5916596B2 (en) 1984-04-16 grant
CA1036455A1 (en) grant
FI58652B (en) 1980-11-28 application
JPS5923356B2 (en) 1984-06-01 grant
DK151231C (en) 1988-07-04 grant
JPS5012381A (en) 1975-02-07 application
JPS548A (en) 1979-01-05 application

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