CH621572A5 - Composition for washing or bleaching textiles - Google Patents

Description

The invention relates to an agent for washing or bleaching textiles, as defined in claim 1.

The use of such a surfactant component, the application concentration of which is preferably 0.15-3 g / 1, in combination with the above-described, cation-exchanging aluminum silicates brings about excellent dirt removal, in particular also for low users

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dung concentrations of 0.15-0.5 g of the surfactant component per liter of wash liquor. The surfactant component used in accordance with the invention is also notable for being particularly insensitive to the hardness constituents of the wash water. s

The surfactants of the amine oxide type used in accordance with the invention are derived from tertiary amines which contain at most two, but generally only one, hydrophobic aliphatic hydrocarbon radical, which is optionally interrupted by heteroatoms and usually has 10-20 C atoms and two 10 short-chain alkyl or alkylol radicals. In these three radicals bonded to the amine oxide nitrogen, there are so many carbon atoms that their total amounts to 12-24 carbon atoms per molecule. Among these amine oxides, those are particularly valuable which, in addition to a total of two methyl and / or 15 or ethyl radicals and / or hydroxyethyl and / or mono- or. Dihydroxypropyl radicals contain a C12-Ci8-alkyl or alkenyl radical. Typical representatives are, for example, the compounds lauryl-dimethyl-amine oxide, lauryl-diethyl-amine oxide, myristyl-dimethyl-amine oxide, myristyl-diethyl-amine oxide, 20 cetyl-dimethyl-amine oxide, cetyl-diethyl-amine oxide. In all of these compounds, at least one of the methyl and / or ethyl radicals can be replaced by the hydroxyethyl, hydroxypropyl or dihydroxypropyl group. The amine oxides with two 25 dihydroxypropyl groups, e.g. the compounds N-dode-cyl- and N-tetradecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide and N-coconut alkyl-N, N-bis (2,3-dihydroxypropyl) amine oxide. Useful amine oxides in which the carbon chain of the hydrophobic residue is interrupted by heteroatoms such as oxygen, nitrogen or sulfur are e.g. the compounds N- (3-dodecyloxypropyl) -N, N-dimethylamine oxide or the amine oxide of N-coconut alkyl-N ', N'-dimethyl-1,3-diaminopropane.

.... ^

The carboxy- and sulfobetaines suitable according to the invention are zwitterionic compounds with a tetrasubstituted, i.e. quaternary ammonium group, which also have a covalently bonded carboxyl, sulfo or sulfate group in the molecule and whose positive and negative 4-fold charge is balanced intramolecularly. Similar to the amine oxides described above, the surface-active betaines have at most two, but generally only one, higher molecular weight aliphatic hydrocarbon radical with a hydrophobic character and at least one, but generally two, lower alkyl radicals with 1-3 carbon atoms, which pass through on nitrogen one or two hydroxyl groups can be substituted or linked directly or via a hetero atom. The anionic, water-solubilizing acid group is connected to the ammonium nitrogen via the fourth substituent, which usually consists of a 5Q short-chain, optionally a double bond or a hydroxyl group-containing aliphatic radical. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane-5J sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropane sulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetra-decyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.

These surface-active betaines can be prepared, for example, by combining the tertiary amine with the hydrophobic long-chain aliphatic hydrocarbon radical and the two lower alkyl or hydroxyalkyl radicals with quaternizing agents, e.g. 3-chloro-2-hydroxypropane sodium sulfonate, 3-chloro-2-hydroxypropyl sodium sulfate, sodium chloroacetate or propane sultone, butane sultone or carbyl sulfate.

60

Also suitable as surfactants are sulfonate betaines in which the anionic, water-solubilizing group is bonded directly to the long-chain, hydrophobic hydrocarbon radical responsible for the capillary activity. Such sulfobetaines can be prepared, for example, from Cg-C20-ci-olefins by reacting them with sulfur trioxide to give a sul-ton and thus quaternizing a tertiary amine with three short-chain aliphatic radicals in a known manner. In a broader sense, the correspondingly substituted quaternary phosphonium and tertiary sulfonium compounds also belong to the class of surface-active betaines.

Suitable fatty alcohol polyglycol ether sulfates according to the invention are the sulfated reaction products of 1-4 mol ethylene oxide with primary or secondary aliphatic C10-C20 alcohols. The aliphatic alcohols suitable as starting materials are preferably the straight-chain primary alkanols and alkenols, which can be of synthetic as well as, in particular, natural origin, but also the so-called oxo alcohols obtainable by hydroformylation of olefins and the secondary alcohols obtainable by paraffin oxidation appropriate chain lengths can be used. Typical representatives of the fatty alcohol polyglycol ether sulfates used according to the invention are e.g. the compounds C12 / C14-coconut alcohol-2-ÄO-sulfate, tallow alcohol-3-ÄO-sulfate, C13-C15-oxoalcohol-3-ÄO-sulfate, Cn-Ci5-sec.-alcohol-3-ÄO-sulfate (ÄO = Ethylene oxide residue).

The surfactant component can also contain anionic surfactants of the soap and sulfonate surfactant type; these are described in more detail below. The surfactant component optionally also contains nonionic surfactants of the ethoxylated aliphatic C10-C20 alcohol type with cloud points above 50 ° C .; this class of compounds is also described in more detail below.

The aluminum silicates defined above can be produced synthetically in a simple manner, e.g. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution. The desired aluminum silicates are also obtained by mixing the two components present in the solid state in the presence of water. Aluminum silicates can also be produced from Al (OH) 3, A1203 or SiOz by reaction with alkali silicate or aluminate solutions. Finally, such substances also form from the melt, but this process appears to be economically less interesting because of the high melting temperatures required and the need to convert the melt into finely divided products. However, the cation-exchanging aluminum silicates to be used according to the invention only form if special precipitation conditions are observed, since otherwise products are formed which have no or inadequate cation-exchange capacity.

The aluminum silicates prepared by precipitation or converted into aqueous suspension in a finely divided state by other processes can be converted from the amorphous to the aged or to the crystalline state by heating to temperatures of 50-200 ° C., however, there is between these two forms with regard to the calcium binding capacity little difference; apart from the drying conditions, this is proportional to the amount of aluminum contained in the aluminum silicates.

The amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. Dry 50-800 ° C. Depending on the drying conditions

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conditions, the product contains more or less bound yeast effect, it is recommended, especially in case of strong water. Anhydrous products are obtained at 800 ° C. If dirty substrates, a certain excess of aluminum - the water is to be completely driven out, this can be used with sodium silicate for one hour, in order to be able to do so in the detached heating to 800 ° C; In this way, the hardness constituents contained in the contaminants are determined in whole or in part AS content of the aluminum silicates. 5 tie. Accordingly, the application concentration of the

Such high drying temperatures for the invented aluminum silicates are preferably in the range of 0.2-10 g AS / 1, and aluminum silicates to be used according to the invention are not particularly 1-6 g AS / 1.

recommend; expediently one does not go over 400 ° C. As already mentioned in the earlier priority applications

out. It is a particular advantage that even with significantly fertilizing, the removal of the contaminants will lower temperatures e.g. 80-200 ° C. to the removal is accelerated and / or significantly improved if one adds a substance to the treatment liquid liquor of the adhering liquid water that can be used in the water for the purposes according to the invention. The calcium thus present as a hardening agent exerts a complexing, varying amounts of bound water and / or precipitating action. As a complexing agent for containing aluminum silicates, after the calcium has been broken down, substances with dried filter cakes are also obtained as fine powders for the purposes of the invention, the primary part of which is so low in its ability to form complexes that it has a maximum size of 0.1 mm, but is usually essential So far not regarded as a typical complexing agent for calcium is lower and down to the fineness of dust, e.g. up to 0.1 | i. has, however, such compounds often have the ability to take into account that the primary particles too large - the precipitation of calcium carbonate from aqueous solutions can be agglomerated to form. Delayed by some manufacturers.

Primary particle sizes in the range of 20 are preferably used. Small amounts of e.g. from 50-1 fi. 0.05-2 g / 1 of complexing or precipitating agent for cal

Aluminum silicates, cium, are used with particular advantage in order to markedly accelerate or improve the removal of the contaminants to at least 80% by weight from particles of a size of 10. In particular, one works up to 0.01 u, preferably from 8 to 0.1 jx. Preferably with additional amounts of 0.1-1 g / 1. These aluminum silicates also contain much larger quantities, no primary or second quantities can be used, but one should use digestive particles above 40 [x. Insofar as it is a matter of the crystalline turn of phosphorus-containing complexation or precipitation mitline products, for the sake of simplicity these will be chosen as quantities such that the phosphorus load is referred to as “microcrystalline”. Wastewater is significantly lower than when using the currently

Common detergents based on triphosphate can be used to form small particle sizes. the precipitation conditions contribute, whereby the 30 complexing or precipitating agents include sol-mixed aluminate and silicate solutions - which are also of the same inorganic nature, e.g. Pyrophosphate, triphosphate, can be fed into the reaction vessel at an early stage - strong higher polyphosphates and metaphosphates.

Exposes shear forces. If the organic compounds according to the invention, which are used as complexing or

Crystallized aluminum silicates used here, so precipitants for calcium are used, the formation of large, possibly penetrating 35 carboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, crystals can be found under the polymers by slowly stirring the crystallizing mass. Carboxyalkyl ethers, polyanionic polymeric carboxylic acids

Nevertheless, an undesired aggio-untj (jeil phosphonic acids) can occur during drying, these compounds mostly occurring in the generation of crystallite particles, so that they are used in the form of their water-soluble salts.

fails, these secondary particles are suitably e.g. by examples of polycarboxylic acids, dicarboxylic acids are the

Also visible in the coarser state, the formulas HOOC- (CH2) „- COOH with n = 0-8, triggering aluminum silicates, which have been ground to the desired grain size as well as maleic acid) methylene malonic acid, citraconic acid , can be used mesaconic acid) itaconic acid, non-cyclic polycarboxylic acids, for example. Mills and / or air classifiers or their combination ^ at least 3 carboxyl groups in the molecule, such as e.g. Tricar

nen. The latter are e.g. at Ulimann: “Encyclopedia of ballvlsäure Aconitsäure Äthvlentetracarbonsäure 113 3-technical chemistry”, volume 1.1951, pages 632-634, be 45 £ allyl acid, Acomtsaure, Ethylenetetracarbonsaure, 1,1,3,3. '' 'Propane-tetracarboxylic acid, 1,1,3,3,5,5-pentane-hexacarboxylic acid,

~ ",. Hexane hexacarboxylic acid, cyclic di- or polycarboxylic acids,

The aluminum, such as e.g. Cyclopentane tetracarboxylic acid, cyclohexane hexacarium silicates of other cations, e.g. those of potassium, bonic acid, tetrahydrofuran tetracarboxylic acid, phthalic acid,

Produce magnesium or water-soluble organic bases in simple terephthalic acid, benzene tri-, tetra- or pentacarboxylic acid rather by base exchange. The use of this50 and mellitic acid.

Compounds instead of sodium aluminum silicates can be useful. Examples of hydroxymono- or polycarboxylic acids are useful if, by specifying the glycolic acid, lactic acid, malic acid, tartronic acid, methyl tar-

Cations achieve a special effect, e.g. The solution tronic acid, gluconic acid, glyceric acid, citric acid, wine condition of simultaneously present tensides influence acid, salicylic acid.

want. These finished, i.e. before use 55. . ,.

Aluminum silicates are used for the A according to the invention, examples of ammocarboxylic acid smd glycine, glycylglycine, purposes alanine, asparagine, glutamic acid, ammobenzoic acid, imi-

nodiacetic acid or triacetic acid, hydroxyethyl-iminodiacetic acid, the amount of aluminum silicate required to achieve a good washing or cleaning ef- ethylenediamine-tetraacetic acid, hydroxyethyl-ethylenediamine-fectes depends on one- 60 triacetic acid, diethylene-triamine-pentaacetic acid and higher levels of it , on the other hand from the homologs, which result from the polymerization of an N-aziridylcarbon amount and the degree of contamination of the acid derivative to be treated, for example of acetic acid, succinic acid, tricarbal

Materials and on the hardness and amount of acrylic acid used, and subsequent saponification, or by condensed water. When using hard water, it is appropriate for polyamines with a molecular weight of 500 to moderate to measure the amount of aluminum silicate so that 65 10,000 with chloroacetic or bromoacetic salts - the residual hardness of the water not more than 5 ° dH ( can be put accordingly.

50 mg CaO / 1), preferably 0.5 to 2 ° dH (5 to 20 mg CaO / 1) Examples of carboxyalkyl ethers are 2,2-oxydibernstein

is. To achieve optimal washing or pure acid and other ether polycarboxylic acids, especially carboxylic

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Polycarboxylic acids containing oxymethyl ether groups, including textiles of all kinds in industry, in commercial corresponding derivatives of the following polyhydric alcohol laundries, in the household.

or belong to hydroxycarboxylic acids, which are wholly or partly. The textiles to be washed can be etherified with glycolic acid in various ways: glycol, thick fibers of natural or synthetic origin, or triglycols, glycerol, di- or triglycerol, glycerol mono- 5 These include, for example, cotton, regenerated cellulose methyl ether, 2,2-dihydroxymethyl propanol, 1,1,1-trihydroxy or linen, and textiles, the highly-refined cotton or methyl ethane, 1,1,1-trihydroxymethyl propane, erythritol, penta- synthetic chemical fibers, such as Contain polyamide, polyester, poly erythritol, glycolic acid, lactic acid, tartronic acid, methyl tartron acrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene acid, glyceric acid, erythronic acid, malic acid, citric chloride fibers. The detergents acid, tartaric acid, trihydroxyglutaric acid, sugar acid 10 according to the invention can also occasionally be used for washing as “easy to care for”

Mucic acid. also known as "non-iron" textiles made of synthetic fiber

Use cotton blend fabrics as transition types to polyanionic polymers.

The carboxymethyl ethers are the sugar, the starch and when washing and cleaning such substrates under

To call cellulose. Use of aqueous, suspended aluminum silicates contains

Among the polyanionic polymers, the polymer cleaning liquors play a special role in the washing or cleaning carboxylic acids, e.g. improve the polymer effect through the usual constituents of such treatment liquors of acrylic acid, hydroxyacrylic acid, maleic acid, itacon. These include, for example: surfactant-like or acid, mesaconic acid, aconitic acid, methylene malonic acid, citra-non-surfactant-like foam stabilizers or inhibitors, tex-cons acid and the like.

Carboxylic acids with each other or with ethylenically unsaturated 20, chemically active bleaches and stabilizers, compounds such as ethylene, propylene, isobutylene, vinyl alcohol, and / or activators for these, dirt carriers, corrosion-inhibiting vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, bitterns, antimicrobial substances, Enzymes, brighteners, color acrylonitrile, methacrylic acid, crotonic acid etc., such as the 1: 1- unc ^ fragrances etc.

Copolymers of maleic anhydride and ethylene or when using one or more of the above, in

Propylene or furan. 25 washing and cleaning liquors usually available

Further polyanionic polymers of the type of polyhydric substances are expediently maintained at the following concentrations of oxypolycarboxylic acids or polyaldehydopolycarboxylic acids:

are essentially composed of acrylic acid and acrolein units or acrylic acid and vinyl alcohol units sub-0-6 g / 1 framework substances punched by copolymerization of acrylic acid and acro-30 0-0.4 g / 1 active oxygen or equivalent amounts of linseed or by polymerization of acrolein and subsequent active chlorine

Cannizzaro reaction, possibly in the presence of formaldehyde. The pH of the treatment liquors can be obtained depending on the. _ _ _. washing or cleaning substrate in the range of 6-13,

Examples of phosphorus-containing organic complexing agents are preferably 8.5-12.

are alkane polyphosphonic acids, amino and hydroxyalkane 35. The invention further relates to the implementation of lyphosphonic acids and phosphonocarboxylic acids, such as e.g. the claimed process certain agents which contain as calcium compounds methane diphosphonic acid, propane-l, 2,3-triphos-binding substances the above-defined aluminum silicates phonic acid, butane-l, 2,3,4-tetraphosphonic acid, polyvinylphos-. These agents are characterized in that they contain phonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino- the surfactant component defined above.

1-phenyl-1,1-diphosphonic acid, aminotrimethylene triphosphone-40 The agents preferably contain 3-40, in particular 3-30 acid, methylamino or ethylaminodimethylene diphosphone% by weight of such a surfactant component.

acid, ethylene-hiaminotetramethylene tetraphosphonic acid, 1 - The aluminum silicate content of such agents can in

Hydroxyethane-l, l-diphosphonic acid, phosphonoacetic acid, range from 5-95, preferably 15-60%. Phosphonopropionic acid, l-phosphonoethane-l, 2-dicarbon- The agents according to the invention can furthermore contain complex acid, 2-phosphonopropane-2,3-dicarboxylic acid, 2-phosphono-formers or precipitants for calcium, the verbutane-1,2, 4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarking, depending on the chemical nature of the agent, preferably bonic acid and copolymers of vinylphosphonic acid at contents of 2-15%.

and acrylic acid. The amount of the agents present in the agents

Through the use according to the invention of the inorganic phosphates and / or organic phosphorus aluminum silicates described above, it should not be greater than a total phosphorus-containing inorganic or organic complexing P content of the agent, even when phosphorus compounds are used 6%, preferably 3%, or precipitant for calcium - readily possible, the other can also in such agents

Phosphorus content of the treatment liquor to a maximum of 0.6 g / 1, usual components of detergents are present, preferably to a maximum of 0.3 g / 1 of organic and / or inorganic. All these percentages are percentages by weight; to keep them ganically bound phosphorus. But it can also "refer in the case of aluminum silicates to water-free working with good success completely phosphorus-free. __ Active substance (= AS).

The process according to the invention, which works using aluminum silicate. The other usual constituents of detergents can be applied in numerous fields, e.g. Use surfactant-like or non-surfactant-like foam stabilization technology and the household for a wide variety of cleaners or inhibitors, fabric softeners, neutral or cleaning tasks. Examples of such alkaline-reacting framework substances, chemically active areas are the cleaning of devices, apparatus, pipe bleach and stabilizers and / or activators for lines and vessels made of wood, plastic, metal, ceramic, these. Components that are usually present in smaller quantities are glass etc. in industry or in commercial companies, e.g. Corrosion inhibitors, antimicrobial substances, cleaning of furniture, walls, floors, objects, dirt carriers, enzymes, brighteners, dyes and fragrances etc. made of ceramic, glass, metal, wood, plastic, cleaning of the composition more typical, at temperatures in polished or painted surfaces in the household etc. A special range of 50-100 ° C textile detergent to be used is an important area of application is washing and bleaching in the area of the following recipe:

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3-3 0% surfactant component as defined above. Also suitable as non-surfactant foam inhibitors

5-70% aluminum silicates (based on AS) are water-insoluble organic compounds such as paraffins

2-45% complexing agent for calcium or halogen paraffins with melting points below

0-50% washing alkalis not capable of complex formation 100 ° C, aliphatic C18 to Qo -ICetone and aliphatic

(= alkaline framework substances) 5 carboxylic acid esters, which are contained in the acid or alcohol residue.

0-50% bleach, as well as other, usually to a lesser extent also in each of these two residues, at least 18 C

additives in textile detergents. Contain atoms (e.g. triglycerides or fatty acid fatty alcohol esters). Alkali-stable silicone oils have also been used for steaming

There now follows an enumeration which has been shown to be useful for use in foam.

Detergent composition suitable according to the invention. Suitable as builders are weakly acidic, neutral, partially and alkaline-reacting inorganic or organic salts.

The anionic surfactants of the soap and sulfo type, which are usable according to the invention, are weakly acidic, neutral or natural surfactants and contain at least one hydrophobic alkaline salt in the molecule, for example the bicarbonates,

organic residue and a water-solubilizing anionic carbonates, borates or silicates of alkalis, alkali sulfates

Group. The hydrophobic residue is usually 15 and the alkali salts of organic, non-capillary,

an aliphatic hydrocarbon radical with 8-26, preferably 2-9 C-containing sulfonic acids, carboxylic acids and wise 10-22 and in particular 12-18 C-atoms or a sulfocarboxylic acid. These include, for example, water-soluble

alkyl aromatic radical with 6-18, preferably 8-16 aliphatic salts of benzene, toluene, xylene or cumene sulfonic acid,

see carbon atoms. water-soluble salts of sulfoacetic acid, sulfobenzoic acid or

Suitable soaps are those made from natural or synthetic 20 sulfodicarboxylic acids.

see, preferably saturated fatty acids, optionally also at the outset as complexing agents or precipitants for alkali metal salts obtainable from resin or naphthenic acids. Calcium compounds are consistently

As surfactants of the sulfonate type, alkylbenzene sulfo substances are useful; you can therefore in the inventive

nate (Cg ^ alkyl), the mixtures known as olefin sulfonates are also present in relatively large amounts than alkene and hydroxyalkane sulfonates and disulfonates, 25 to fulfill their function as complexing agents or precipitation

as is necessary for example from monoolefins with end or medium for calcium.

internal double bond by sulfonation with gaseous ^ Yes. ..,, ^ ..,. ,,

_ c,. . ff, f ,. , ",. , j The components of the preferably as textile detergent or

like sulfur trioxide and subsequent alkaline or acidic. TT,. . . ,. ö ^, _,, J. ,

Hydrolysis of the sulfonation products is considered. As products to be used as household cleaning agents, alkanesulfonates which are derived from alkanes by sulfo- 30 ®ond ^ re Je. Framework substances are usually selected so that chlorination or sulfoxidation and subsequent hydrolysis Jass react neutral to vigorously alkaline, so that u ■ vT 4. t * a. ' u j and w * jjv ™ c the pH value of a 1% solution of the preparation mostly in or neutralization or by bisulfite addition to olefins «• u„ ^,.,, ^.

u. , XXT .. t ~, c .. range is 7-12. For example, Delicates are mostly available. Other useful surfactants of the sulfonate type ^, TT w

• i j »T-i, o c *. * ■" DJ- o ir .. neutral to weakly alkaline reaction (pH = 7-9.5),

are the esters of a-sulfofatty acids, e.g. the a-sulfonic acids, r, JT ^ i,

u a - ~ 4. A / f 4-t. i j v, yr, -nii while soaking, prewashing and cooking detergents strong or dry acid AthyleStem ^ K ° k ° S -'Palmkem "35 alkaline (pH = 9.5-12, preferably 10-11.5)

... ". Are higher pH for special cleaning purposes

If the surfactant compo values used in the invention are desired, these can be obtained from the alkali silicates of suitable Ma2Q: Si02 ratios or from by using any nonionic surfactants which may be present

Set the type of the ethoxylated aliphatic C10-C20 alcohols with Trü-caustic alkalis easily.

Practice points above 50 ° C by reacting 1 40 rrr-1, ^, -TTTT Z

"X, S As,, 0 t v", ® Among the m H202 water used as bleach

Obtained moles of alcohol with 8-20 moles of ethylene oxide. Derar- ..., u. ,,,, "r«

.... .. j, A • t_ t,, supplying compounds have the Natnumperborat-tetrahy-

Current oxygenation products are made up of polymer homologues drat (NaBo2.H2o2-3H20) and the monohydrate

Connections in a known statistical distribution. / XT ^ Tr o \ l j ^ ^, _. , ..,. a x • j -r »^ (NaBQ2 * H2Q2) special meaning. But there are also typical ethoxyher products of this type are e.g. C12 / C14-,; T ^ ^,,? ^ u coconut alcohol-10-ÄO; Tallow alcohol-14-EO (iodine number of tallow-containing boxates can be used, e.g. perborax alcohol = 0.5); Oleyl- / Cetylalkohol-I0-Ä0 (iodine number of the Al- 4H202. These compounds can be used completely or by, I _ x by other active oxygen carriers, in particular ° ° S by peroxyhydrates, such as peroxycarbonates (Na2C03 • 1.5 The foaming power of the Surfactants can be increased or decreased by combination H202), peroxypyrophosphates, citrate perhydrates, urea nation of suitable surfactant types; a 5Q H2Q2 or melamine H202 compounds as well as by H202 reduction can also be achieved by adding non-surfactant-providing persistent salts such as caroates ( KHS05), achieve perbene-like organic substances.Zoate or peroxyphthalate can be replaced.

A reduced foaming power, which is recommended when working in is ", usual water-soluble and / or water-

Machines are desired, can often be achieved by combination-insoluble stabilizers for the peroxy compounds together of various types of surfactants, e.g. the sulfonates with Nonio-J5 with these in amounts of 0.25-10% by weight. As sneezing and / or with soaps. In the case of soaps, the foam damping increases water-insoluble stabilizers, which e.g. 1-8, preferably with the degree of saturation and the C number of the fatty acid residue; Make up 2-7% of the weight of the entire preparation

Soaps of the saturated C2o_24 fatty acids are therefore particularly suitable as foam suppressants, which are usually obtained by precipitation from aqueous solutions. _ Magnesium silicates MgO: Si02 = 4: 1 to 1: 4, preferably

The non-surfactant-like foam inhibitors include 60 2: 1 to 1: 2 and in particular 1: 1. In their place are other chlorine-containing N-alkylated aminotriazines, the alkaline earth metal, cadmium or tin silicates correspondingly usable by reacting 1 mole of cyanuric chloride with 2-3 moles of composition. Water-containing oxides of a mono- and / or dialkylamine with 6-20, preferably tin, are also suitable as stabilizers. Water soluble stabilizers

Receives 8-18 carbon atoms in the alkyl radical. A similar effect is provided by propoxifiers which are present together with water-insoluble and / or butoxylated aminotriazines, e.g. Products that can do 65 are the organic complexing agents, the amount of which can be obtained by adding 5-10 moles of propylene oxide to 1 mole of 0.25-5, preferably 0.5-2.5% by weight of the total

Melamine and other attachments of 10-50 moles of butylene oxide can make up preparations.

receives this propylene oxide derivative. To wash already at temperatures below

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80 ° C, especially in the range of 60-40 ° C, use a satisfactory starch product, e.g. To achieve a reduced bleaching effect, preference is given to activator starch, aldehyde starches etc. Polyvinylpyrrolidone-containing bleaching components are also incorporated into the preparations. useful.

As activators for perverbin delivering H202 in water. The enzyme preparations to be used are usually a fertilizer. Certain enzyme mixtures with different effects, e.g. Pro-forming N-acyl, O-acyl compounds, especially teases, carbohydrases, esterases, lipases, oxidoreductases, acetyl, propionyl or benzoyl compounds, as well as carbon catalases, peroxidases, ureas, isomerases, lyases, trans acid or Pyrocarbonate. Useful compounds are ferases, desmolases or nucleases. Of particular interest are among others: N-diacylated and N, N'-tetraacylated esse are those from bacterial strains or fungi such as Bacillus amines such as e.g. N, N, N ', N'-tetraacetyl-methylenediamine or 10 subtilis or Streptomyces griseus enzymes obtained, in particular - ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluene special proteases or amylases, the Relatively resistant and amide, for example, to alkali, per-din or 1,3-diacylated hydantoins, alkyl-N-sulfonyl-carbon compounds and anionic surfactants N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl- are still effective at temperatures up to 70 ° C.

Benzamide, N-methyl-N-mesyl-p-nitrobenzamide and N-methyl enzyme preparations are usually

N-mesyl-p-methoxybenzamide, N-acylated cyclic hydrazides, 15% solutions of the active ingredients or as powders, granules or

acylated triazoles or urazoles such as e.g. the monoacetylmalein ais marketed cold atomized products. They contain

acid hydrazide, 0, N, N-trisubstituted hydroxylamines such as e.g. as a blending agent, often sodium sulfate, sodium chloride,

0-benzoyl-N, N-succinyl-hydroxylamine, 0-acetyl-N, N-succi-alkali ortho-, pyro- or polyphosphates, especially tripoly-

nyl-hydroxylamine, 0-p-methoxybenzoyl-N, N-succinyl-hydrophosphate. Particular emphasis is placed on dust-free preparations;

xylamine, 0-p-nitrobenzoyI-N, N-succinylhydroxyIamin and 20 they are obtained in a manner known per se by incorporating

0, N, N-triacetyl-hydroxylamine, N, N'-diacyl-sulfurylamide, oily or pasty nonionics or by granulation such as e.g. N, N'-dimethyl-N, N'-diacetyl-sulfurylamide, and N, N'- with the help of melts of water containing salts in their own

Diethyl-N, N'-dipropionyl-sulfurylamide, triacylcyanurates, e.g. Crystal water.

Triacetyl or tribenzoyl cyanurate, carboxylic anhydrides, enzymes can be incorporated which are suitable for e.g. Benzoic anhydride, m-chlorobenzoic anhydride, 25 certain types of dirt are specific, for example proteases

Phthalic anhydride, 4-chlorophthalic anhydride, sugar or amylases or lipases; preference is given to using

esters such as Glucose pentaacetate, 1,3-diacyl-4,5-diacyloxy combinations from enzymes of various effects, in particular imidazolidines, for example the compounds 1,3-diformyl combinations of proteases and amylases. 4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imide- The detergents can be used as optical brighteners for tree

azolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine, acy-30 especially derivatives of diaminostilbene disulfonic acid, such as e.g. Contain tetrapropionylglycoluril or di- or their alkali metal salts. Suitable are e.g. Salts acetyl-dibenzoylglycolunl, diaçylated 2,5: diketopiperanzine, the 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -

such as. 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-stilbene-2,2'-disulfonic acid or compounds of the same structure

diketopiperazine, l, 4-dipropionyl-3,6-dimethyl-2,5-diketopipe-, which instead of the morpholino group a diethanolamine

razin, acetylation or bezoylation products of propy- 35 nQ group, a methylamino group or a 2-methoxyethyl

Wear lendi urea or 2,2-dimethyl-propylene diurea (2,4,6,8- amino group. As brighteners for polyamide fibers

Tetraaza-bicyclo (3,3, l) -nonane-3,7-dione or its 9,9- those of the type of 1,3-diaryl-2-pyrazolines in question, for example

Dimethyl derivative), sodium salts of p- (ethoxycarbonyloxy) - as the compound l- (p-sulfamoylphenyl) -3- (p-chlorophe-

benzoic acid and p- (propoxycarbonyloxy) benzenesulfonic acid. nyl) -2-pyrazoline and compounds of the same structure,

The active chlorine compounds 40 serving as bleaching agents which instead of the sulfamoyl group e.g. the methoxycarbonyl, 2-

can be inorganic or organic in nature. Methoxyethoxycarbonyl, acetylamino or vinyl sul

The inorganic active chlorine compounds include fonyl groups. Useful polyamide brighteners are also

Alkali hypochlorites, which in particular in the form of their mixed salts, are substituted aminocoumarins, e.g. the 4-methyl-7-dime

or addition compounds to orthophosphates or to thylamino- or the 4-methyl-7-diethylaminocoumarin. Further condensed phosphates such as, for example, on pyro and poly 45 brighteners and polyamide brighteners, the compounds 1- (2-benzimi-

phosphates or alkali silicates can be used. dazolyl) -2- (l-hydroxyethyl-2-benzimidazolyl) ethylene and 1-

Contain the washing and washing aids monopersulfate ethyl-3-phenyl-7-diethylamino-carbostyril usable. As and chlorides, active chlorine forms in aqueous solution. Brighteners for polyester and polyamide fibers are the

In particular, 2,5-di- (2-benzoxazolyl) thiophene, 2- (2-benzoxazolyl) - come as organic active chlorine compounds

the N-chlorine compounds in question, in which one or the other naphtho [2,3-b] thiophene and 1,2-di- (5-methyl-2-benzox-

two chlorine atoms are bonded to a nitrogen atom, azolyl) ethylene being suitable. Furthermore, brighteners of the type preferably the third valence of the nitrogen atoms to one of the substituted 4,4'-distyryldiphenyl may be present; e.g.

negative group leads ^ in particular to a CO- or SO2-dje compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Also

Group. These compounds include dichloro- and tri-mixtures of the above-mentioned brighteners can be used chlorocyanuric acid or its salts, chlorinated alkyl guanides 55 or alkyl biguanides, chlorinated hydantoins and chlorinated

Melamine. Of particular practical interest are inventive

In the preparations according to the invention, moderate agents of powdery to granular nature can also be used

Dirt carriers are included, which are produced from the fibers by all methods known in the art

Keep dirt suspended in the liquor so that graying can become 60.

prevent. Water-soluble colloids are mostly organic for this purpose. the powdery aluminum silicates suitable in shear nature, such as the water-soluble simple way with the other components of the detergent

Mix salts of polymeric carboxylic acids, glue, gelatin, salt of ether, whereby oily or pasty products such as carboxylic acids or ether sulfonic acids of starch or Cel e.g. Nonionics onto which powder is sprayed. Another lulose or salts of acidic sulfuric acid esters of cellulose 65 can be prepared by incorporating the powdered

or strength. Water-soluble, acidic groups also contain aluminum silicates in the other, as aqueous slurry.

Polyamides are suitable for this purpose. Further components of the agent, which are then crystallized

soluble starch preparations and other than the above operations or by drying the water in the heat in

621 572

8th

a powder is transferred. After hot drying, e.g. on rollers or in atomization towers, heat and moisture sensitive components can then be incorporated, e.g. Bleaching components and activators for these, enzymes, antimicrobial substances, etc.. 5

Examples

With regard to the production of the aluminum silicates used and determination of the calcium binding capacity, reference is made to the above-mentioned earlier priority patent applications. All 10% figures are percentages by weight; in the case of aluminum silicates, they refer to water-free active substance (= AS). The water contents were determined by heating the products to 800 ° C. for one hour.

The following is a list of 15 aluminum silicates which can be used according to the invention:

I: 0.9 Na20 • 1 A1203 • 2.04 Si02 • 4.3 HzO (= 21.6% HzO) fully crystalline

Calcium binding capacity: 150 mg CaO / g AS 20

Ia: 0.9 Na20 • 1A1203 • 2.04 Si02 • 2.0 H20 (= 11.4%

H20)

II: 0.8 Na20 ■ 1 A1203 • 2.655 Si02 • 5.2 H2Q fully crystalline

Calcium binding capacity: 120 mg CaO / g AS 25

IIa: 0.8 Na20 • 1A1203 • 2.65 Si02 • 0.2 H20 III: 0.9 Na.O • 1 A1203 • 2.04 Si02 • 47 H20 X-ray amorphous

Calcium binding capacity: 160 mg CaO / g AS V: 1.5-1 A1203 • 2 Si02 ■ 3 H20 (= 14.4% H20) 30

X-ray amorphous

Calcium binding capacity: 140 mg CaO / g AS VI: 0.9 Na20 • 1 Ai203 • 2.04 Si02 • 6.7 H20 (= 6% H2Q) X-ray amorphous

Calcium binding capacity: 145 mg CaO / g AS 35

VII: 1 Na20 • 1 A1203 • 2 Si02 • 1H20 (= 6% H20) X-ray amorphous

Calcium binding capacity: 150 mg CaO / g AS VIII: 0.8 NazO • 1A1203 • 2.65 Si02 • 4 H20

X-ray amorphous 40

Calcium binding capacity: 60 mg CaO / g AS IX: 1 Na20 • 1A1203 • 1 Si02 • 1.4 H20 X-ray amorphous

Calcium binding capacity: 120 mg CaO / g AS X: 1 NazO • 1 A1203 • 5 Si02 • 2.8 H20 45

X-ray amorphous

Calcium binding capacity: 100 mg CaO / g AS

The salt-like constituents contained in the detergents in the examples - salt-like surfactants, other organic salts and inorganic salts - were present as sodium salts, unless expressly stated otherwise. The related names or abbreviations mean: «KA-2ÄO-sulfate», «TA-3ÄO-sulfate»; the sulfated reaction products of coconut fatty alcohol C12 / C14 (KA) or tallow alcohol (iodine number = 0.5) (TA) with 2 or 3 moles of ethylene oxide (ÄO);

"Amine oxide": the compound N- (3-dodecyloxypropyl) -N, N-dimethylamine oxide;

"Amine oxide II": the compound N-tetradecyl-N, N-bis (2,3-di-hydroxypropyl) amine oxide;

"Carboxybetaine": the compound N-tetradecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate;

“Sulfobetaine”: the compound 3- (N-dodecyl-N, N-bis (2,3-di-hydroxypropyl) ammonium) propane sulfonate;

“ABS”: the salt of an alkylbenzenesulfonic acid obtained by condensing straight-chain olefins with benzene and sulfonating the resulting alkylbenzene with 10-15, preferably 11-13, carbon atoms in the alkyl chain; “Olefin sulfonate”: a sulfonate obtained from α-olefin mixtures with 15-18 C atoms by sulfonation with SO 3 and hydrolyzing the sulfonation product with alkali, which essentially consists of alkene sulfonate and hydroxyalkanesulfonate, but also also contains small amounts of disulfonates;

"Ester sulfonate": a sulfonate obtained from hydrogenated tallow fatty acid methyl ester by sulfonation with S03;

"TA + 14 ÄO": the adduct of 14 moles of ethylene oxide (ÄO) with a technical tallow fatty alcohol (iodine number = 0.5) (TA);

“Soap”: contains a hardened mixture of equal parts by weight of tallow and rapeseed oil fatty acid (Pie— C22) as the fatty acid component;

"CMTS": the salt of O-carboxymethyl-tartronic acid; «EDTA»: the salt of ethylenediaminetetraacetic acid; "NTA": the salt of nitrilotriacetic acid;

"CMC": the salt of carboxymethyl cellulose.

The following table contains formulations of some detergents according to the invention, the formulations 1, 2 and 3 being full detergents which are preferably used in the household, in commercial enterprises and in industry for washing colored or white textiles at temperatures of 40-100.degree of 50-100 ° C can be used. Formulations 4 and 5 relate to perborate-free preparations for laundry up to 60 ° C.

XI:

approx. 1 NazO • 1 A1203 • 6 Si02 • 3.2 H20

component

% Of detergent

X-ray amorphous

according to example

Calcium binding capacity: 60 mg CaO / g AS

50

1

2nd

3rd

4th

5

XII:

0.9 NazO • 1 A1203 • 2 Si02 • 3 H20 (= 11% H20)

KA-2ÄO sulfate

fully crystalline

- -

15.0

-

-

-

Calcium binding capacity: 160 mg CaO / g AS

TA-3ÄO sulfate

12.0

-

-

5.0

-

XIII:

0.28 NazO • 0.62 K20 • 1A1203 • 2.04 Si02 • 4.3 H20

Amine oxide I

-

-

7.0

-

-

fully crystalline

55 amine oxide II

-

-

-

5.0

-

Calcium binding capacity: 170 mg CaO / g AS

Carboxybetaine

-

5.0

-

-

-

XIV:

1.5-1 A1203 • 2 Si02 • x H20

Sulfobetaine

-

-

-

-

12.5

X-ray amorphous

SECTION

-

-

-

-

7.5

Calcium binding capacity: 120 mg CaO / g AS

Olefin sulfonate

-

-

8.0

-

XV:

1.5 -1 A1203-2 Si02 • x H20

60 ester sulfonate

3.0

-

-

-

-

fully crystalline

TA-14ÄO

-

-

5.0

-

-

Calcium binding capacity: 170 mg CaO / g AS

Soap

2.0

3.0

2.0

2.0

3.4

XVI:

1.5-1 B203 • 2 Si02 • 1.5 H20

Foam inhibitor

0.9

0.8

0.3

-

0.6

predominantly crystalline

Aluminum silicate I

30.0

-

-

-

-

Calcium binding capacity: 120 mg CaO / g AS

65 aluminum silicate V

-

35.0

-

-

-

XVII:

0.92 Na20 • 1 A1203 • 1.8 Si02 -3.71 H20

Aluminum silicate VII

-

-

30.0

-

-

fully crystalline

Aluminum silicate XII

-

-

-

50.0

-

Calcium binding capacity: 180 mg CaO / g AS

Aluminum silicate XVII

-

-

-

-

35.0

9

621 572

component

% Constituent in the detergent according to Example 12 3 4

Na5P3O] 0

5.0

-

8.0

-

-

CMTS

-

-

-

-

7.5

NTA

-

4.3

-

-

-

EDTA

0.3

-

0.2

0.2

0.2

Na20 ■ 3.3 Si02

4.0

4.0

3.5

4.5

3.5

Na2C03

-

-

7.0

6.5

NaBOz • H202 • 3 H20

25.0

23.0

26.0

-

-

MgSi03

1.3

1.5

2.0

-

-

CMC

1.9

1.5

1.6

1.9

1.6

Rest: sodium sulfate and water

Nas Na5P3O10 can be replaced by the same amount of a P-free phosphate substitute, e.g. replace the salts of citric acid or O-carboxymethyl-tartronic acid.

Example 6

A detergent which is highly effective for washing at temperatures of 40-60 ° C and at application concentrations of 1.5-3 g / 1 has the following composition:

20.0% amine oxide I 3.2% soap

30.0% aluminum silicate V 0.3% EDTA 5.0% citrate 6.0% Na20 • 3.3 SiOz 5 7.5% Na2C03

1.5% CMC remainder to 100% sodium sulfate and water.

Example 7

io A detergent intended for washing in particularly hard water has the following composition:

20.0% sulfobetaine 4.5% ester sulfonate 2.6% soap

0.3% foam inhibitor 30.0% aluminum silicate VII 10.0% Na5P3010 0.3% EDTA 2.0% magnesium silicate 3.5% Na20-3.3Si02 22.0% NaB02 • H202 • 3 H20 1.6% CMC Rest up to 100% sodium sulfate and water.

20th

25th

c

Claims (9)

621572 2nd PATENT CLAIMS 1. Agent for washing or bleaching textiles with a content of finely divided, water-insoluble, capable of binding the hardness constituents of water, containing a calcium-binding capacity of at least 50 mg CaO / g of water-free active substance, containing bound water-containing silicates (Kat2, 'nO) x • Me203 • (Si02) y, in the cat a calcium-exchangeable cation of the valence n, x is a number of 0.7-1.5, Me boron or aluminum and y is a number of 0.8-6, as a phosphate substitute and with a surfactant content, thereby characterized in that it is a surfactant component composed of 1 part by weight of one or more surfactants from the group of the surface-active amine oxides, carboxybetaines, sulfobetaines and fatty alcohol polyglycol ether sulfates and up to 3 parts by weight of anionic sulfonate surfactants, soaps and / or ethoxylated aliphatic Ci0-C20 alcohols with cloud points above 50 ° C contains. 2. Composition according to claim 1, characterized in that the index number y in the formula for the water-insoluble silicates means the value 0.9-4. 3. Composition according to claim 1 or 2, characterized in that the water-insoluble silicates contain sodium, lithium, potassium, ammonium, magnesium or water-soluble organic bases, in particular sodium, as cations. 4. Composition according to one of claims 1 to 3, characterized in that the water-insoluble silicates are aluminum silicates and the composition 0.7-1, l (Kat2 / nO) • AI203 • 1.3-3.3 Si02 and have a calcium binding capacity of 100-200 mg CaO / g AS, with compounds of the composition 0.7-1.1 Na20 • A12Os • 1.3-2.4 SiOz can be preferred. 5. Composition according to one of claims 1 to 4, characterized in that the water-insoluble silicates at least 80 wt .-% consist of particles of a size of 10-0.01 (x, preferably 8-0.1. 6. Composition according to one of claims 1 to 5, characterized by a content of the surfactant component in amounts of 3-40 wt .-%. 7. Composition according to one of claims 1 to 6, characterized in that it contains the silicates in amounts of 5-95, preferably 15-60 wt .-%. 8. Composition according to one of claims 1 to 7, characterized in that it additionally contains complexing agents or precipitants for calcium, in particular of the following types: meta- and polyphosphates, and polycarboxylic acids, hydroxycarboxylic acids, amino carboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and Phosphonic acids, preferably in the form of their water-soluble salts. 9. Composition according to claim 1 to 8, characterized in that its composition is within the following recipe: 3-30% by weight surfactant component 15-60% by weight water-insoluble silicates (based on the anhydrous substance) 2-45, preferably 2-15 wt .-% complexing agent for calcium 0-50% by weight washing alkalis not capable of complex formation 0-50% by weight of bleach and other additives, which are usually present in small quantities in textile detergents. 5 10. Agent according to one of claims 1 to 9, characterized by a content of organic and / or inorganic phosphorus compounds in such quantities that the total P content of the agent does not exceed 6% by weight and preferably 3% by weight. 10th The older priority document CH-A-602 961 describes a process for washing, bleaching or cleaning solid materials, in particular textiles, in which these materials are treated with a liquor in which finely divided water-insoluble, a calcium binding capacity of at least 50 mg of CaO / g of water-free active substance (= AS) containing optionally bound water containing 20 compounds of the general formula (Kat2 / nO) x • Me203 • (Si02) y in the cat a cation exchangeable with calcium of the valence n, x a number of 0.7-1.5, Me boron or aluminum and y a number of 0 , 8-6, preferably 1.3-4, are suspended. Sodium is preferred as the cation; but it can also be replaced by hydrogen, lithium, potassium, ammonium 30 or magnesium and the cations of water-soluble organic bases, e.g. those of primary, secondary or tertiary amines or alkylolamines with a maximum of 2 carbon atoms per alkyl radical or a maximum of 3 carbon atoms per alkylol radical. 35 For the sake of simplicity, these cation-exchanging compounds which are used instead of the phosphates, in particular tripolyphosphate, are referred to as “aluminum silicates”. Sodium aluminum silicates are preferably used, but all the information given for their production and use applies analogously to the other claimed compounds. Preferred aluminum silicates have the composition 45 0.7-1.1 Na20 • A1203 • 1.3-2.4 Si02. According to the earlier priority patent application, aluminum silicates are also of the composition 50 0.7-1.1 NazO ■ A12Q3 •> 2.4-3.3 Si02 of particular practical interest. The two types of aluminum silicate, which differ in their crystal structures, have a calcium binding capacity in the range of 100-200 mg CaO / g AS. The application concentration of these aluminum silicates in the treatment liquors can be in the range of preferably 0.2-10 g AS / 1, in particular 1-6 g AS / 1. According to the other details of the earlier priority patent applications mentioned, the washing and cleaning effect of the process can be improved by the fact that the treatment liquors also contain surfactants as usual constituents.