DE2544035A1 - METHOD OF WASHING TEXTILES, AND MEANS OF CARRYING OUT THE METHOD - Google Patents

Description

Henkel & Cie GmbH

Patent department

4000 Düsseldorf, the 2 "). Scpter. ^ E-: << 75 ^Dr * ^öhk

Henkelstrasse 67 _{'r, n} * _r

/ Ο 4 A U 0 0

Patent application D 5000

"Ancestors for washing textiles, as well as means for.; Carrying out the process"
"'Addition to the patent' {patent application P 24 12 837.8 (D 4642/4787/4819))

That. Main patent (patent application P 24 12 837.8

(-D 4642/4787/4819)) relates to a method for washing, bleaching or cleaning of solid materials, especially textiles, by treating these materials with a Liquor which contains substances capable of binding the hardness components of the water, the process is characterized by that in the aqueous treatment liquor a calcium binding capacity of at least 50 mg CaO / g anhydrous Finely divided, water-insoluble, optionally bound water containing active substance (- AS) tending compounds of the general formula *

^(Cat 2 / n ^0> x / ^Me 2 ° 3 * ^ ¹ Vy (D

in the cat a cation of valency exchangeable with calcium η, χ is a number from 0.7 to 1.5, Me is boron or aluminum and y is a number from 0.8 to 6, preferably from 1.3 to 4, are suspended. Through the process of the main patent, it is possible to use the washing and cleaning process up to now to replace related calcium complex-binding phosphates in whole or in part.

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Henkel & Cie GmbH

Sheet 2 for patent application D 50Ö0 'Palentabteilung

The calcium binding capacity of the compounds defined above can reach values of 200 mg CaO / g AS and is often preferred in the range of 100 - 200 mg CaO / g AS.

The above-defined compounds capable of binding calcium are hereinafter referred to as "aluminum silicates" for the sake of simplicity. This also applies in particular • for the preferred sodium aluminum silicates to be used; all information given for their production and processing apply mutatis mutandis to the entirety of the connections defined above.

The preferred cation is sodium; but it can also replaced by hydrogen, lithium, potassium, ammonium or magnesium or the cations of water-soluble organic bases e.g. by those of primary, secondary or tertiary amines or alkylolamines with a maximum of 2 carbon atoms per alkyl radical or at most 3 carbon atoms per alkylol radical.

An additional patent (patent application P 24 12 839.0 (D 4716)) to the main patent relates to an improvement of the method described in the main patent, which consists in the fact that the aqueous Treatment liquor for the textiles in addition to those defined above Alum'iniumsilikaten a surfactant component from 1 part by weight of nonionic and 0-3 parts by weight of anionic Contains surfactants, the nonionic surfactants being a mixture of different degrees of athoxylation, an aliphatic hydrocarbon radical with 10-18 carbon atoms containing compounds, in which per part by weight of nonionic compounds with 8-20 ethylene glycol ether residues in the molecule, 0.2-2 parts by weight of compounds with 2-6 ethylene glycol ether residues in the Molecule are present. By combining the aluminum silicates with the surfactant component described above, an improved soil removal, especially with greasy and oily soiling.

609815/1388

Henkel & Cie GmbH

Sheet 3 of the patent application D 5000 “Palentabteilung

As stated in the main patent, the removal the impurities are significantly improved if a substance is added to the treatment liquor that reacts to the im Calcium, which is present as a hardness component, has a complexing effect and / or exerting effect. It has now been found that a number of such compounds are very special Dimensions are suitable for use in the process or in smocks of the main patent. The subject of the invention is accordingly a further embodiment of the process for washing and bleaching textiles by treating them with an aqueous one Liquor containing substances capable of binding the hardness builders of the water, according to the main patent in the

aqueous treatment liquor

Calcium binding capacity of at least 50 mg CaO / g anhydrous Finely divided, water-insoluble, optionally bound water-containing compounds of the general formula

(Cat _{2 / n} O) _x · Me ₂ O ₃ . (SiO ₂ ) _y (I)

in the cat a cation of valency exchangeable with calcium η, χ a number from 0.7 - 1.5, Me boron or aluminum and y a Number from 0.8 to 6, preferably from 1.3 to 4, suspended and an organic calcium complexing or precipitating one Structural substance are included and where appropriate, the aqueous treatment liquor also contains a surfactant component; it is characterized in that one of the following compounds is used as a structural substance - as a free acid or as a Water-soluble salt capable of binding calcium - present:

SS 1 δ / Ii-S 8

Henkel & Cie GmbH

Sheet U for patent application D 5000 ■ Patent department

A. An azacycloalkane-2,2-diphosphonic acid of the formula

(CH ₂ ) _n PO ₃ H ₂

II

PO ₃ H ₂

in the η for 3-5 and R for a hydrogen atom or a Alkyl group with 1-3 carbon atoms;

B. A cyclic aminophosphonic acid of the general formula

<"R ₁ - N PO (OH)

yy .NHR ₁

O = C C

^ Vo (OH)

in which R stands for an alkyl radical with 1-6 carbon atoms or a Hydrogen atom and η represents a number from 1-3;

C. A pyrrolidone-5,5-diphosphonic acid, containing the hydrogen atom can be replaced on the nitrogen by an alkyl radical with 1-6 carbon atoms;

D. A copolymer of a monounsaturated, with a Carboxylic acid esterified monoalcohol with maleic acid or maleic anhydride in a ratio of 1: 1, the anhydride units being essentially hydrolyzed under use conditions are.

E. Poly (c £ -hydroxyacrylic acid) with a molecular weight of at least 20,000.

F. A copolymer of a polyvinyl alkyl ether and maleic acid or maleic anhydride, the alkyl radical containing 1-6 carbon atoms and the anhydride units being essentially hydrolyzed under the conditions of use.

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Henkel & Cie GmbH

Sheet 5 to patent application D 5000, patent department

G. 3-Amino-1-hydroxypropane-1. _t .1-diphosphonic acid H. A polyphosphonic acid of the general formula

Vo ₃ H ₂

χ ι?

in which X is H, OH, NH ₂ or Cl and Y is H or halogen;

I. A citric acid pyrolysate, all of the compounds A-I are water-soluble and / or water-soluble salts enabled bonds. ... ..

The azacycloalkane-2,2-diphosphonic acids of the above Formula are in the unpublished German patent

(Patent application P 23 43 196.1 (D 4779)) described, As detailed in the earlier patent, they can be prepared by using lactams of the specified type Formula, in which, however, instead of the diphosphonomethylene group a carboxyl group is present, with phosphorus trihalides or phosphorous acid and phosphorus trihalides reacted, the reaction product hydrolyzed and optionally converted into a water-soluble salt. As examples of this Group of compounds may be mentioned: Azacycloheptane-2,2-diphosphonic acid, Azacyclopentane-2,2-diphosphonic acid; N-methylazacyclopentane-2,2-diphosphonic acid and azacyclohexane-2,2-diphosphonic acid.

6098 ι S / 13 8 8

BATH ORIGINAL

Henkel & Qe GmbH

Sheet 6 to the patent application '^ 5000' patent department

The cyclic aminophosphonic acids of the general formula II are in detail in the unpublished German patent

(Patent application P 23 43 195.0 (D 4682)) described; they can be prepared by the process specified there, in which dicarboxylic acid derivatives of the formula X - (CH) _n - X, where η = _{1-4 and X = CN, COONH 2} or COONHR (R = alkyl radical with 1-4 C. Atoms) mean, reacts with phosphorus trihalides or phosphorous acid and phosphorus trihalides, the reaction product is acid hydrolyzed and optionally converted into a water-soluble salt. The reaction of the dicarboxylic acid derivatives with the phosphorus compounds usually takes place in a ratio of 1: 2 to 1: 6, preferably in a ratio of about 1: Individual examples of this class of compounds are 2-hydroxy-2 _> 7 - dioxo-3-amino-3-phosphono- 1,2-azaphosphacycloheptane; 2-hydroxy-2-oxo »3-amino-3-phosphonyl-5-oxo-1,2-azaphosphacycloheptane; 2-hydroxy-2-oxo-3-amino-3-phosphonyl-6-oxo-1,2-azaphospha cyclohexane; 1-Kethyl-2-hydroxy-2-oxo-3-methylamino-3-phos-phonyl-6-oxo-1, 2-azaphospha cyclohexane; 1-ethyl-2-hydroxy-2-oxo-3-ethylamino-3-phosphonyl-6-oxo-1,2-azaphosphacyclohexane; 1-butyl-2-hydroxy-2-oxo-3-butylamine-3-phosphonyl-6-oxo-1,2-azaphosphacyclohexane and 1-methyl-2-hydroxy-2-oxo-3-methylamino-3-phosphonyl -7-oxo-1,2-azaphosphacycloheptane.

The pyrrolidone-5,5-diphosphonic acid as \\ ^r ie their alkyl-substituted derivatives thereof on the nitrogen atom are described in German patent (Patent Application P 23 43 147.2 (D 4692)). It can be prepared, for example, by reacting succinic acid derivatives, such as succinic acid diamide, which optionally has an alkyl radical having 1-6 carbon atoms in each amido group, with phosphorus trihalides or phosphorous acid and

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Hang! & CieGrr.bH

Sheet 7 for patent application D 500C A ^ ** C / / HOC

Phosphorus trihalides and subsequent alkaline hydrolysis of the reaction product take place. In addition to the 'compound with R = H, there are in particular the methyl, ethyl, propyl and Butyl derivatives in question.

The copolymer of esterified unsaturated monoalcohol with Maleic acid. Or maleic anhydride is preferably derived from a monounsaturated primary alcohol with 3-4 carbon atoms, especially from allyl alcohol, the one with ■ a straight-chain or branched-chain carboxylic acid with 1-6 carbon atoms in the molecule is esterified. The carboxylic acid is in particular acetic acid or propionic acid. A preferred product, the copolymer of allyl acetate and maleic anhydride in a ratio of 1: 1, is commercially available. The product has a molecular weight in the range between 4,000 and 10,000, but they are also products with higher molecular weights suitable.

Poly (Oi-hydroxyacrylic acid) is from Solvay & Cie., Brussels available. Their production is described in DOS 2,161,727, for example. The molecular weight of poly- (e £ ~ hydroxyacrylic acid) is generally above 20 and in particular 26 OdO. Have particularly proven themselves Products with molecular weights in the order of 100,000 to 140,000. Also higher molecular weight compounds up to to the limit of water solubility are suitable.

As polyvinyl alkyl ether / maleic anhydride (or maleic acid) copolymers Copolymers in which the alkyl group has 1-6 carbon atoms are suitable. The monomer ratio is 1: 1. The molecular weight is at least about 1,500, but is generally higher and can, for example range between 100,000 and 2,500,000. A preferred commercial product is "Gantrez AN - 119" with an average molecular weight of 250,000 that of from GAF Corporation, New York, USA.

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Henkel & Cie GmbH

Sheet 8 for patent application ^ 5000 §> Patent department

Important representatives of the compounds of the formula III are given in the examples (see below). ' * y c / / η ο c

“Citric acid pyrolysate” is a commercial product from Citrex S.A., Belgium (La Citrique Beige) which is on the market under the name "Citrex". It is a product that is produced in the pyrolysis of a citric acid alkaline earth salt is obtained when the salt is at temperatures in the range between about 250 C - 400 C to ■ • to increase the titratable alkalinity and then Hydrolysis of the salt with the formation of the unsaturated satire is obtained. The product is believed to be a mixture of compounds and has approximately 4 or more carboxyl groups per molecule on average. Particularly suitable and included in the term "citric acid pyrolysate" is a product which is obtainable by adding bisulfite to the acid prepared as described above.

All of the compounds used according to the additional patent are solids in anhydrous form. however, they are in in practice often used with a certain water content or in aqueous solution. Quantities relate to nevertheless on the anhydrous compounds.

In general, the compounds A - I are in ionized form in aqueous solution; they are mostly in shape Their water-soluble salts are used. 3. the cations of the alkali metals, in particular of sodium and potassium are present, but also ammonium and / or organic ammonium derivatives are present. The cations derived from water-soluble organic bases that come into question, are, for example, those of primary, secondary or tertiary amines or alkyl oil amines with a maximum of 2 carbon atoms derived per alkyl radical or at most 3 carbon atoms per alkylol radical are.

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Henkel & Cie GmbH

Sheet 9 to the patent application D 5 OO 0 St patent department

The invention also relates to the implementation of the method suitable agents, which are characterized in that they contain at least one of the above-mentioned compounds as Contain structural substance.

The use of the compounds listed above as complexing agents in the proceedings bzv /. in the means of the main. patents is especially for phosphate-free or low-phosphate products significant. According to the invention, excellent phosphate-free detergents and cleaning agents can be produced. So far these still contain phosphorus-containing compounds, the phosphorus content is compared to the previously used phosphate-containing compounds Detergents considerably reduced. The invention thus makes a contribution to solving the problem caused by an oversupply So-called phosphate problems caused by phosphate in standing water in particular.

The agents according to the invention preferably contain at least one surfactant. The composition typically at temperatures in the range of 50 - 100 ⁰ C to-use laundry detergent is in the range of the following formulation:

5-40, especially 5-30 % anionic and / or

nonionic and / or zwittenionic surfactants,

5 - 70 % aluminum silicates

2 - 45 % of the calcium-binding compounds used according to the invention

0 - 50 % washing alkalis not capable of complex formation (= alkaline structural substances)

O - 50 % bleach and other additives, usually in smaller quantities in laundry detergents.

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609315/1388

Henkel & Ge GmbH

BlatflQ for patent application ^D 5000 Jt (J) patent department

The aluminum silicates described are synthetically produced products that can be easily produced, e.g. by reacting water-soluble silicates with Prepare water-soluble aluminates in the presence of water permit. Aqueous solutions of the starting materials can be used for this purpose mixed with one another or one component present in the solid state with the other, as an aqueous solution present component to be implemented. By mixing the two components, which are present in a solid state, are obtained in the presence of water, preferably with comminution of the mixture, the desired aluminum silicates.

The water-containing products obtained in this way are initially X-ray amorphous; they can be aged or converted into the crystalline state by heating to temperatures of 50 - 200 ° C. in the presence of water. The amorphous or crystalline aluminum silicate obtained as an aqueous suspension during production can be removed from the remaining by filtration; Separate aqueous solution and dry at temperatures of 50 400 C, for example. Depending on the drying conditions, the product contains more or less bound water. The AS contents of the ¹ aluminum silicates are determined by heating to 800 ° C. for one hour. '- -

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609815/1388

Henkel & Cie GmbH

Sheet 11 to the patent application ' ^D 5OCO' patent department

Such high drying or dewatering temperatures are not recommended for the aluminum silicates to be used according to the invention. It is a particular advantage that dried products can be used for the purposes according to the invention even at significantly lower temperatures of, for example, 80-200 ° C. until the adhering liquid water has been removed. The aluminum silicates produced in this way and containing varying amounts of bound water are obtained as fine powders after the dried filter cake has been divided up, the primary particle size of which is not more than 0.1 mm, but is usually much lower and down to dust fineness, for example up to 0.1 μ. goes. It must be taken into account here that the primary particles can be agglomerated to form larger structures. It is easily possible to manufacture products with primary particle sizes in the range of 30 ~ 1 μ .

It is particularly advantageous to use aluminum silicates which are at least 80% by weight of particles with a size of 10 0.01 μ-, preferably 8-0.1 μ. exist. These aluminum silicates preferably contain no primary or secondary particles above 30/6. As far as these are crystalline products, these are referred to as "microcrystalline" for the sake of simplicity.

Precipitation conditions can already contribute to the formation of small particle sizes mixed aluminate and silicate solutions - which can also be fed into the reaction vessel at the same time - are strong Exposed to shear forces. If the crystallized aluminum silicates which are preferably used according to the invention are produced, then so • one prevents the formation of large, possibly penetrating crystals by slowly stirring the crystallizing ones Dimensions. ''

603815/1388

Hang! & Cie GmbH

Sheet 12 to the patent application ■. ^D 5000 · Patent Department

Nevertheless, undesired agglomeration of crystallite particles can occur during drying, so that it is advisable to pass these secondary particles in a suitable manner, for example through. Air separations to remove. Even in a coarser condition occurring aluminum silicates, which are ground to the desired grain size. can be used. Mills and / or air separators or their combinations are suitable for this purpose. The . the latter are described, for example, in Ulimann: "Enzyklopadie der technischen Chemie" Volume 1, 1951, pages 632-634.

Besides the particle size of the aluminum silicates, the age or crystallization state of the aluminum silicates can also influence their calcium binding capacity? it is preferred products used with a calcium binding capacity iia Bareich 100-200 mg CaO / g AS; of these, in turn, the crystalline types are preferred. A calcium binding capacity in the specified range is found primarily in compounds with the following composition: ■ ■

O _f 7-1.1 Na ₂ O. Al ₂ O ₃ . 1.3-3.3 SiO ₃ .

; This sum formula comprises two different types of crystalline aluminum silicates or their X-ray amorphous precursors. These two types differ in their crystal structures (to be recognized by the X-ray diffraction diagram. £>. ^T TL ^T n) and in their compositions. These are:

«.) 0.7-1.1 Na ₂ O. Al ₂ O ₃ . 1.3-2.4 ß) 0.7-1.1 Na ₂ O. Al ₂ O ₃ . _y 2.4-3.3

Even with the use of aluminum silicates with a less high Calcium binding capacity is a considerable improvement of the products or the washing result by the invention used compounds achieved.

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Henkel & Cie GmbH

Sheet 5 for patent application ^D 5000 'patent department

Even products that are still wet immediately after precipitation or even be in suspension, may be advantageous for the purposes of this invention; it can for example

a) a still flowable suspension of the aluminum silicate in the lye in which it is at the end of the manufacturing process is located.

b) an aluminum silicate from which the mother liquor was partially separated,

c) a still flowable suspension of the resulting after partial or complete washing out of the mother liquor Aluminum silicate in water, or

d) an aluminum silicate from which the wash water has been partially separated,

be used.

What has been said about the primary particle size applies to aluminum silicates that are still moist or in suspension or as a slurry corresponding.

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Henkel & Cie GmbH

Sheet 1 h to the patent application ^ 5000 _ patent department

To achieve a good washing or cleaning effect required amount of aluminum silicate depends on the one hand on its calcium binding capacity, on the other hand on the amount and the The degree of soiling of the materials to be treated and the hardness and amount of water used. Using from hard water it is expedient; the amount of aluminum silicate to be dimensioned so that the residual hardness of the water is not more than 5 ° dH (corresponding to 50 mg CaO / 1), preferably 0/5 to 2 ° dH (.5 to 20 mg CaO / 1). In order to achieve an optimal washing or cleaning effect, it is particularly recommended in the case of heavily soiled substrates / to use a certain excess of aluminum silicates in order to ensure that those in the to bind detached impurities contained hardness builders in whole or in part. Accordingly, the application concentration of the aluminum silicates in the range of preferably 0.2-10 g AS / 1, in particular 1 - 6 g AS / 1 are.

It is preferable to use small additional amounts of, e.g. 0.05 - 2 g / l of compounds used according to the invention, in order to accelerate or improve the removal of the impurities noticeably. In particular, you work with additional amounts of 0.1-1 g / l. Also much bigger ones Quantities can be used, but you should use the phosphorus-containing complexing or. Select precipitants in such amounts that the phosphorus pollution of the wastewater is significantly lower than when it is used the z. Currently common detergents based on triphosphate. With a higher proportion of those used according to the invention Compounds, the proportion of silicates in the wash liquor can be correspondingly lower.

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Hang! & Cie GmbH

Sheet 15 to patent application D 5000 'patent department

By using the aluminum silicates described above together with the compounds used according to the invention it is easily possible to check the phosphorus content of the treatment liquors even when using phosphorus-containing compounds to a maximum of 0.6 g / l, preferably to a maximum of 0.3 g / l of organically and / or inorganically bound phosphorus to keep. However, it can also be worked entirely free of phosphorus with good results.

That. according to the invention, using synthetic, preferably Crystalline alurainium silicates working process is used for washing textiles of all kinds in industry, suitable in commercial laundries and in the household.

The textiles to be washed can consist of a wide variety of fibers of natural or synthetic origin. These include, for example, cotton, regenerated cellulose or linen as well as textiles, the highly refined cotton or synthetic chemical fibers, such as polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers contain. The detergents according to the invention - (see below) can also be used for washing the as "easy-care", Occasionally produce textiles called "non-iron" from synthetic fibers and cotton blended fabrics.

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Henkel & Cie GmbH

Blati 6 'to the patent application L) 5000 * patent department

When washing and cleaning such substrates after the claimed In the process, the washing effect can be improved by customary constituents of such treatment liquors. to • 'These include in particular surfactants, surfactant-like or non-surfactant-like foam stabilizers or inhibitors, fabric softeners, chemically acting bleaching agents as well as stabilizers and / or activators for these, dirt carriers, corrosion inhibitors, antimicrobial substances, enzymes, brighteners, dyes and fragrances, etc.

When using one or more of the above in wash liquors The following concentrations are expediently observed for substances that are usually present:

0-2.5 g / l surfactants,

0 - 0.4 g / l active oxygen or equivalent amounts of Active chlorine.

under "active oxygen" or "active chlorine" are here Understood bleaching compounds with oxygen-oxygen bond or chlorine content, the amount given being pure arithmetically based on oxygen or chlorine.

Depending on the substrate to be washed, the pH of the treatment liquors can be in the range from 6-13 _r, preferably in the range from 8.5-12.

By adding the agents according to the invention to water According to the invention to be used washing liquors for textiles formed. The information on the proportions and the nature of those present in the treatment liquors Compounds accordingly also apply to the agents according to the invention.

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Henkel & Cs3 GmbH

Blatt ") 7 to the patent application D 5000 'Pa'xr.Sabteilung

The amount of the compounds of the phosphonic acid type present in the agents according to the invention is preferably no greater than a total P content of the agent of 6 %, preferably 3 % t . The percentages are percentages by weight. Unless otherwise stated, they generally refer to anhydrous substances.

The calcium complex-binding and / or precipitating compounds used according to the invention are preferably present in the agents according to the invention in amounts of 2-15 % . However, they can also be used in smaller amounts, for example 1 %, or in larger amounts, for example 15-30. The weight ratio of the substances used according to the invention to the silicates of the formula I is frequently about 1: 8 to 2: 1.

,% Wherein relatively low depending on the type and amount of the compounds used in the invention aluminum silicate levels (.z B - the aluminum silicate content of such agents can range from 2-95 Ge \} ~% are, in general it is between 5 and 95 wt.. . of 5-15 %) or relatively high contents (e.g. 15-60 %) may be preferred.

The surfactant combinations used according to patent (patent application P 24 12 839.0 (D 4716)) are preferably used as surfactants used in which low and high ethoxylated compounds, possibly in combination with anionic Surfactants are present. The nonionic surfactants (= nonionics) to be used afterwards are addition products of 2-6 resp. 8-18 Get ethylene oxide on 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide. Particularly The purely aliphatic alcohols, e.g. coconut or tallow fatty alcohols, oleyl alcohol or secondary alcohols are important Alcohols with 8-18, preferably 12-18 carbon atoms, derived Nonionics.

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Henkel & Cie GmbH

Sheet 18 to the patent application D 5000 patent department

Hatches from

The attachment products can also be used as nonionics Use ethylene oxide on terminal or internal vicinal alkanediols, preferably those with 2-4 or v /. 8-14 Ethylene glycol ether residues in the molecule.

The agents according to the invention can also contain organic, non-capillary-active sulfonic acids containing 1-8 carbon atoms, Carboxylic acids and sulfocarboxylic acids are present; here- ■ to include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, Sulfur benzoic acid or sulfodicarboxylic acids.

Wash alkalis are also preferably used in the process of the invention or in agents according to the invention. These then make usually about 2-35 wt -.% Of the total composition of. The term "V / ash alkalis" includes, in particular, the carbonates, bicarbonates, borates and silicates of the alkali metals, preferably of sodium. Soda and sodium silicate, which are often used together, are particularly important washing alkalis. The alkali silicates usually have SiO ₂ / NapO ratios in the range between 0.66: 1 to k: 1, ratios between 2.3: 1 and 3.5: mostly being preferred. Which SiO2 / Na ₂ O ratio is preferred in particular also depends on how large the desired contribution of the alkali silicate to the alkalinity of the detergent or the liquor is. Ratios in the range between 1: 1 and 2.3: 1 can therefore also be particularly expedient.

With regard to the rest for use in the inventive Agents and surfactants suitable in the process according to the invention, Foam inhibitors, foam stabilizers, bleaches and stabilizers and / or activators for these, dirt carriers, enzymes and brighteners, reference is made to the main patent in which the above-mentioned classes of compounds have been carefully considered. The main patent also contains further information on * the aluminum silicates that can be used and other details that also apply to the procedures and means of the invention apply.

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Henkel & Cie GmbH

Page 19 for patent application D 5000 _Jfe ^ 'patent department

154 * 035,

ractical ii

Of particular practical interest are according to the invention Means of powdery to granular nature, which are produced by all processes known in the art can. To facilitate the assembly and handling of the products, it can be useful to use the connections of the formula I to be used in the form of agglomerates. It is generally useful if these agglomerates in use, for example with regression of the primary particles,

'disintegrate. Also with regard to the production of the invention Reference is made to the main patent.

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Qt \ Henkel & Cie GmbH

BlatßO for patent application D 5000, patent department

Examples

It will first manufacture one for the purpose of. Invention suitable finished aluminum silicate , • described for which no protection is sought here. It deals ., is a microcrystalline product. Further examples for the production of suitable aluminum silicates are given in the main patent. The aluminum silicates described there can be used according to the invention in exactly the same way as that dealt with in more detail below Aluminum silicate:

The deionized with Water-diluted aluminate solution is mixed with the silicate solution while stirring vigorously. Both solutions were at room temperature » It was formed as the primary precipitation product with an exothermic reaction an X-ray amorphous sodium aluminum silicate. The water content was determined by heating the product for one hour determined at 800 ° C.

After 10 minutes of vigorous stirring with a high speed Intensive stirrer (10,000 rpm; make "Ultraturrax" from Janke & Kunkel, IKA-Werk, Stauffen / Breisgau, Federal Republic Germany) the suspension of the amorphous precipitation product was transferred to a crystallization vessel, where the formation of large crystals was prevented by stirring the suspension. After sucking off the lye from the Crystal slurry and washing with deionized water until the washing water running off had a pH value of approx. 10, the filter residue was dried, then ground in a ball mill. The grain size distribution was with Determined with the help of a sedimentation balance.

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Henkel & Cig GmbH

Sheet 21 for patent application D 5000 'patent department

Manufacturing conditions for the aluminum silicate (Im)

Precipitation: 2.985 kg of the aluminate solution of the composition

17.7 % Na O, 15.8% Al O, .66.6 % H ₂ O 0.15 kg caustic soda. 9.420 kg water '

^ 2.445 kg one made from commercially available water

glass and slightly more alkali-soluble

¹ freshly prepared silica,

25.8% sodium silicate solution of the composition 1 Na 0. 6.0 SiO_

Crystallization: 6 hours at 90.degree. C. Drying: 24 hours at 100.degree

Composition: 0.9 Na "0. 1 Al ₉ O. 2.04 SiO_. 4.3 HO

' (= 21.6% HO)

Degree of crystallization: fully crystalline

Calcium binding capacity: 170 mg CaO / g AS.

The particle size distribution determined by sedimentation analysis was in the following range:

> 40 μ. - 0% ■ Maximum of the particle size _{- <10 /} a = 85 - 95% distribution curve: 3 - 6 / i.

<8 μ. = 50 - 85%

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609815/1388

Hang! & Cie GmbH.

Blatß2 for patent application -. D 5000 'fsient department

The degree of crystallization of an aluminum silicate can be 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 Determine crystallized products.

.All% figures are percentages by weight. "'..- ·

The calcium binding capacity of the aluminum silicates was determined in the following way:

1 l of an aqueous solution containing 0.594 g of CaCl ₂ '(= 300 mg CaO / l = 30 ° dH) and adjusted to a pH of 10 with dilute NaOH is mixed with 1 g of aluminum silicate (based on AS The suspension is then vigorously stirred for 15 'at a temperature of 22 ° C. (-2 ° C.) After filtering off the aluminum silicate, the residual hardness χ of the filtrate is determined. From this, the calcium binding capacity is calculated in mg Ca0 / g AS according to the formula: (30 -χ) «10.

(AS = active substance)

609815/1388

Henkel & Cie GmbH

BIaU 2 3 for patent application ^D 5000. Potential development

The salt-like constituents contained in the washing detergents or auxiliary washing agents - salt-like surfactants, other organic salts and inorganic salts - were present as sodium salts ₇ unless expressly stated otherwise. In particular, all of the compounds formulated below as free acids were used in the form of their sodium salts. _if the related terms or abbreviations mean:

"ABS" the salt of a straight-chain condensation Olefins with benzene and sulfonation of the resulting alkylbenzenes. Alkylbenzenesulfonic acid obtained with 10-15, preferably 11-13 carbon atoms in the Alky chain;

"Fs-ester sulfonate" is a hardened one from the methyl ester Tallow fatty acid sulfonate obtained by sulfonation with S0_

"Olefinsulfonat" means a mixture of straight-chain internal ones Olefins with 12-18 carbon atoms by sulfonating with.S0_ and hydrolyzing the sulfonation product with Lye obtained sulfonate, which essentially consists of alkene sulfonate and oxyalkanesulfonate, but also contains small amounts of disulfonates;

"OA + χ A'O" or ' ¹ TA + χ ÄO "are the addition products of ethylene oxide (XO) with technical oleyl alcohol (OA) or tallow fatty alcohol (TA) (JZ = 0.5), the numbers for χ denote the molar amount of ethylene oxide added to 1 mole of alcohol;

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Hang! & C: e GmbH

BIatt2A door patent application D 5000 'patent department

"TA-Sulphate" is the salt of a sulphated, essentially saturated one produced by the reduction of tallow fatty acid Fatty alcohol;

, "CMC" the salt of carboxymethyl cellulose;

"Perborate" is a product containing about 10% active oxygen with the approximate composition NaBO ₂ · H ₂ O ₂ . 3

"Foam inhibitor" an N-alkylated aminotriazine from the Reaction of cyanuric chloride with mono- or dialkylamine with 8-18 carbon atoms in the alkyl radical;

"Aluminum silicate" means a microcrystalline aluminum silicate prepared as described above, where the percentages relate to the weight fraction of the anhydrous active substance;

"NA-silicate" means a sodium silicate with an Si0 ₂ / Na ₂ 0 weight ratio of 3.35: 1;

"Soap C ^ ₂ -C ₂₂ or Soap ^ gC ^ g" Salts of fatty acids with the specified number of carbon atoms.

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6 ü 3 8 1 5 Al 3 8 8

Henkel & Cis GmbH

Blatt2 5 for patent application ^ 5000 'Palci.lnbtcilung

"EDTA" the salt of ethylenediaminetetraacetic acid;

"PHAS" the salt of the poly (pc-Hydr ο xyacryl acid) Manufacturer: Solvay & Cie., Belgium; Molecular weight in the '' order of magnitude of 100,000 - 150,000.

"Citric acid pyrolysate" is a pyrolysis product of citric acid with an average of four carboxyl groups in the form of reacted with sodium bisulfite prepared as described above ' Pyrolysis product. Manufacturer: Citrex S.A. Belgium;

"" Allyl acetate / MSA "is a linear 1: 1 copolymer made from allyl acetate and maleic anhydride, wherein the maleic anhydride groups are hydrolyzed. Molecule ar gev / icht in the range 4,000 10 000.

"Vinyl methyl ether / MA" a copolymer in which vinyl methyl ether and hydrolyzed maleic acid units are present in a ratio of 1: 1. Molecular weight 250,000.

Some recipe examples for V / a schmitt el according to the invention now follow.

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6Ü9815 / 13S8

Sheet £ 6 for patent application D 5000

Henkel & Cie GmbH

Patent department

Components example 1 Soap C ₁₂ -C ₂₂ 3.0 DA + 5 AO 3.0 ) xoal alcohol C-] 2-15 ⁺ ^ ^ ⁰ 8.0 : mc 1.5 BDTA 0.2 5g SiO ₃ 1.5 jpt. Brightener 0.3 Aluminum silicate 30.0 iosodium silicate 4.0 ^ itric acid pyrolysate 10.0 read Na ₂ SO ^ + H ₂ O

Components Examples 3 2 5.0 Olefin sulfonate 8.0 2.0 ΓΑ-sulfate 2 _S 5 Soap C ₁₆ -C ₁₈ 2.0 4.0 OA + 10 AO 1.5 CMC 1.5 0.2 EDTA 0.2 1.5. Mg SiO, 1.5 0.15 opt. Brightener 0.3 1.0 Foam inhibitor 1.0 25.0 Perborate 30.0 20.0 Aluminum silicate 27.0 10.0 soda 7.0 10.0 Na-silicate 7.0 Vinyl methyl ether / MSA 10.0 8.0 Citric acid pyrolysate Remainder Na «S0 ^ + H ₂ O

Instead of vinyl methyl ether / MA, allyl acetate / MA could also be used with the same success. .

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Sheet27 for patent application D 5000

Henkel & Cie GmbH

Patent department

Components

Examples 5 6

-15 ⁺

7 AO

Olefin sulfonate
Fs-ester sulfonate
Soap C ₁₂ -C ₂₂
Soap C ₁₆ -C ₁₈
TA + 5 EO _;
TA + 14 ÄO
OA + 5 AO
Oxo alcohol C

IDTA

tg SiO ₃

opt. Brightener
Show inhibitor
^p erborat

Aluminum silicate
soda
Na-silicate.

1 -.Hydroxy-1-phenyl-

nethane diphosphonic

acid

1-arnino-p-chlorophenylnethane diphosphonic acid

3-amino-1-hydroxypropane-1,1-diphosphonic acid

2-Hydroxy -2,7-dioxo-3-amino-3-phosphono-T, 2-azaj) hosphacycloheptane

¹ IeSt Na ₀ SO, + water

8.0

4.0

1.5 2.5

1.5 0.2

1.5 0.15

25.0 25.0

15.0 6.0 8.0

2.0

3.0 1.5 0.2 1.5 0.3 1.0

30.0 30.0 7.0 7.0

4.0

7.0 3.0

3.0

1.5

0.2

1.5

0.15

0.5 20.0 15.0 15.0 '

2.5

4.0

3.0

3.0

8.0 1.5 0.2

1.5 0.3

8.0 12.0 13.0

10.0

035

_

6 U 9 ti 1 S / -1388

Henkel & CieGrub:> S.

PaJeoV department

Sheet? 8 for patent application D 5000

Instead of 2-hydroxy ~ 2, 7-phosphacycloheptane were also - in the same amount of weight azacycloheptane-2,2-diphosphonic acid or pyrrolidone-2,2-diphosphonic acid is used instead of 1-hydroxy-1-phenylmethanediphosphonic acid also 1-hydroxy-p-chloi-phenylmethanediphosphonic acid, instead of i-amino-p-chlorophenylinethanediphosphonic acid also 1-amino-i-phenylmethanediphosphonic acid.

Components Examples 3.0 8 9 Soap C ₁₂ -Cp ₂ 2.0 TA + 5 ÄO 3.0 3.0 TA + 14 ÄO 7.0 8.0 OA + 5 AO 1.5 Oxo alcohol. C _1? _ _ir + 7 ÄO 0.2 CMC 1.5 1.5 EDTA 0.2 0.3 Mg SiO ₃ 1.5 opt. Brightener 0.25 8.0 Perborate 30.0 12.0 Aluminum silicate 15.0 13.0 soda 20.0 12.0 Na-silicate 15.0 Yinyl methyl ether / MSA PHAS 15.0 Remainder NapSO / + HpO.

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B! Atf29 for patent application

5000

Hang! & CSe G: nb! -!

Patent Department 2544Π35

Components Examples 8.0 10 * 11 SECTION 4.0 Olefin sulfonate 8.0 ΰθΐΧ θ U ^ 0 "" ^ OO 5.0 O ti JL J- L- t ^ j ^ IR 2.0 TA + 14 ÄO 1.5 Oxo alcohol C _12-1 ^ + 7 AO 3.0 0.2 CMC 1.5 1.5 EDTA "■ 0.2 0.15 Mg · SiO ₃ ¹ »5 0.4 opt. Brightener 0.3 25.0 Foam inhibitor 1.0 25.0 Perbooat 30.0 15.0 Aluminum silicate 30.0 7.0 Na-silicate 3.0 Citric acid pyrolysate 10.0 Balance Na ₂ S0 _{/ f} + H ₃ O

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Sheet 3O to patent application D 5OOO

Henkel & Cis GmbH

component Example 12 TA + 5 EO ^; 2.0
3.0 TA + 14 ÄO 7.0 CMC 1.5 EDTA 0.2 Mg SiO ₅ 1.5 opt. Brightener 0.25 Perborate _ 20.0 Aluminum silicate 15.0 soda 20.0 Ma-silicate 15.0 1-chloro-1-phenylmethanediphos-
phonic acid 8.0 ^ est Na ₂ SO / + H ₂ O

609815/1383

Henkel & Cie GmbH

Sheet 31 for patent application D 5000 patent department

In Examples 4, 8 and 12 the combinations are the Components A, B and C with the particularly advantageous Combined surfactant combinations in which nonionic compounds with 8-20 ethylene glycol residues in the molecule are combined with nonionic compounds which have 2-6 ethylene glycol ether residues per molecule, with optionally anionic surfactants are present in addition to the nonionic compounds.

Most of the recipes given - all those that contain perborate - are mainly intended for use as the above-mentioned heavy-duty detergents for hot laundry (approx. 95 C), while the recipes without perborate, especially washing at medium temperatures, such as at 60 ⁰ C relate. Of course, the detergents of the first-mentioned group can also be used with good success at higher temperatures, or they can also be used as mild detergents. In the context of the invention, however, mild detergents according to the invention usually have higher surfactant proportions than the heavy-duty detergents described in the examples.

Since the detergents of the invention according to any, in Let processes known in the art be produced, a detailed description of the production is dispensed with been.

6ÜS815 / 1388

Claims (1)

1. Further training in the washing and bleaching process of textiles by treating them with an aqueous liquor, which was able to bind the hardness components of the water Contains substances, according to patent patent application , Ρ 24-12 837.8 (D 4642/4787/4819)) in the aqueous "treatment liquor a calcium binding capacity of at least 50 mg CaO / g anhydrous active substance (= AS), finely divided, water-insoluble, optionally bound water-containing compounds of the general formula (Cat _{2 / n} O) (SiO ₂ ) (I) in the cat a cation of valency exchangeable with calcium η, χ is a number from 0.7 to 1.5, Me is boron or aluminum and y is a number from 0.8 to 6, preferably from 1.3 to 4, suspended and an organic calcium complexing resp. precipitating builder substance are contained and where optionally the aqueous treatment liquor also contains a Teiiside component, characterized in that one of the following compounds is used as the structural substance as a free acid or as a water-soluble one Salt with calcium binding capacity is present, A. An azacycloalkane-2,2-diphosphonic acid of the formula (CH ₉ ) 2 ^Y n PO-H ₅ II PO ₃ H ₂ in the η for 3-5 and R for a hydrogen atom or a Alkyl group with 1-3 carbon atoms; 6 ü 3 8 1 5 / 4-388 Henkel & Cig GmbH Btatt 3 -> to the patent application ~ j 5000 ralu.tabteilung 25UO35 B. A cyclic aminophosphonic acid of the general formula R ₁ - N PO (OH) III