CH636124A5 - Easily disintegrating, water-insoluble detergent-builder agglomerate in particle form - Google Patents

Description

The present invention relates to a readily disintegrating, water-insoluble detergent builder agglomerate in particle form.

The known detergents based on linear higher 60 alkylbenzenesulfonates and pentasodium tripolyphosphate as builders have so far been recognized for their good washing action, whereby the linear higher alkylbenzenesulfonates were biodegradable and showed an excellent washing action, while the polyphosphates were regarded as good and safe builders for the detergent . However, since phosphates have been less valued in recent years because of their perceived threat to eutrophication of inland waters and because of legal regulations,

3 636124

attempts have been made to use numerous other phosphate substitutes with a rapid dispersion of the zeolite powder

Builders properties to use, such as by adding this powder in finely divided

Carbonates, silicates, borax, the trisodium salt of the nitrilotries form to the wash water, preferably before the

acetic acid (NTA), organic sequestering agents, polyelectrolyte, the detergent components of which are added. It can

Chelating agents and other products, of which 5 are added to the other components of the detergent.

took that they give the cleaning effect synthetic, organic and are mixed with these dry components,

shear detergents. Most of these so that the separate addition to the wash water does not require

However, phosphate substitutes have disadvantageous properties. However, separate dimensions and allowances are

although they are not as strong and time-consuming for eutrophication of the inland areas and are unsuitable for domestic use, as is attributed to phosphates. Some io suitable. A separate addition of the zeolite powder to the other phosphate substitutes are poisonous, others become cancer-prone dry detergent components can lead to an

attributed to stimulating properties, others are not uniformly distributed to form a layer or are too stable or impart undesirable flow to the end product - a different kind of separation of the detergent components.

Properties, give processing difficulties, while lead due to the particle size, the zeolite powder have another bad smell or react with the 15 other detergent components usually in the lower region of the detergent container. As a result, there is considerable uncertainty as to whether and how much is available when the detergent is used for the first time, and which products are used as suitable phosphate substitutes; this results in different and can be seen. disadvantageous properties when using the detergent.

20 In addition, the finely divided zeolite powder at

It has recently been found that zeolites and release cause dust problems due to the small particle size.

especially certain synthetic, amorphous zeolites and men lead.

crystalline molecular sieve zeolites preferably in at least the object of the invention is to overcome these disadvantages of partially hydrated form despite their insolubility in water and to propose a better detergent,

are suitable ion exchangers for calcium ions and consequently which is dust-free and does not separate and which also shows the washing power of synthetic, organic detergents, has an acceptable uniform appearance and improves special inorganic detergents and also does not have the disadvantageous properties of spray-dried non-detergents. ionic detergents can be used. If- detergents or detergents with subsequently

has water-insoluble zeolites and, in particular, sodium-substituted molecular sieve zeolites and that there are no suitable builders without minium silicates and the washing power can be difficult to produce on an industrial scale.

measurably improve, so that they are partly used as a phosphate substitute. It is known from DT-OSP 2 535 792 that it can be used non-ionically and in some cases the phosphates in the case of visible detergents are completely adsorbed by adsorption on a crystalline Na commercial heavy-duty detergent To replace potassium aluminum silicate, however, it has been found that because of their insolubility in sorbents they tend to have a higher silica content than the previous ones, the water hardness forming ions are slower to ss and are less suitable as scaffold deactivators than the polyphosphates, especially if they are original. The Dutch patent application 75/10 506 is originally in its anhydrous form. Furthermore, the agglomeration of zeolites with mixtures of hy-in many cases deposits on textiles, which are known with such hydrated salts.

Zeolites containing detergents have been washed. In order to achieve the object according to the invention, a slightly spray-dried heavy-duty detergent shows that the insoluble, water-insoluble detergent builder Ag.

Zeolites are increasingly suggested to have abglomerate in particulate form on the washed laundry, which

store, presumably because the molecular character of spray drying is such that it contains 10 to 90% by weight of finely divided

Form sieve zeolites into larger particles which are not as easily dispersible as zeolite builders, which do not exchange calcium ions, as subsequently added zeolites of the general formula with a final particle size below 15 μm. This 45

presumably rests on the fact that the zeolites are due to the silicate (M20) • (Al203) y • (Si02) z • wH20

structure are more closely connected. These zeolites are consequently retained by the textiles and, in many cases, in particular in the case of colored textiles, result in a metal ion selected from the group consisting of a pleasant white shimmer. Furthermore, since the zeolite particles mean 50 sodium and potassium,

of the other components of the spray-dried washing y a value of 0.8 to 1.2,

by means of being held fairly firmly, they will also be released more slowly z to a value of 1.5 to 3.8 and to the wash water and cannot so quickly have a value of 0 to 9, the partial

trap the ions resulting in water hardness. Although one obtains a particle diameter of less than 15 microns, a better builder effect if the zeolite particles are very small. From 90 to 10% by weight of a binder for the aforementioned are small and in the micron - and below the micron range - are zeolite particles, whereby the binder is selected from and therefore goes into the wash liquor faster than if it is in a group consisting of water-soluble starches, non-ionic spray-dried beads, and in particular in surfactants, various gums, sugars, synthetic ores that contain silicates. Although the possible deposition of ganic polymers and mixtures thereof, and given - of zeolite powder on colored laundry then does not result in any difficulty if up to 10% by weight of free moisture is present, which leads to difficulties if the laundry is washed after washing. Agglomerate particles have a sieve number of 4 to 180 meshes of which the circulation is dried, the washing having the US standard sieve series.

mechanical scrolling and the vigorous swirling with The invention also covers the spray-dried products, dry air is freed from zeolite powder, there are always difficulties with this particulate detergent content when washing the laundry to dry on 65 agglomerates of building materials. Although the use of a water line is preferred, when it is preferred to hang up moist binders or binders that are soluble on the hanger, it is also possible to

is used, especially after washing with cold melting binder, at the temperature

Water. of the wash water melt or otherwise together

636124

4th

break and which, if they are used, are usually isolated with stalling medium and will then be used on a water-soluble component. Air dried at normal temperature so that its water content

The used in the mixtures according to the invention in a range from 5 to 30% and preferably 15 to 22%

Zeolites are generally crystalline, amorphous and mixed. Due to the way in which the crystalline / amorphous zeolites natural or synthetic zeolites used according to the invention are produced, the moisture content of this mo

Origin or mixtures thereof, which are quick and molecular sieves but up to 0% at the start of production,

Effective against the water hardness ions as the zeolite acts during mixing with the binder. Products are preferably used which, in the presence of water, have a more desired shape,

quickly with the cations causing the hardness, such as in an at least partially hydrated state

Calcium, magnesium, iron and the like react and the io is converted.

Soften the washing water before other reactions with it- The zeolites used as molecular sieves are said to mostly contain ions and the detergent components. Which do not contain any adsorbed gases such as carbon dioxide because

Ion exchange capacity for calcium ions in the case of zeolites containing gas leads to an undesirable foaming-these products in a range from 200 to 400 mg equiva- lents, if the detergent containing zeolite is brought into contact with lent calcium carbonate hardness per g of aluminum silicate or higher than water. In some cases, however, and preferably in a range of 250 to 350 mg equivalents, this foaming is tolerable or even desirable.

lenten per g. The zeolites are in a finely divided state with a

The water-insoluble crystalline aluminum silicates have a final particle size of less than 15, for example between mostly a lattice of pores of essentially the same size in 0.005 to 15 and preferably in a range of 0.01 to 10.

a range from 3 to 10 and mostly 4 Â, this size being 2 <> in particular from 0.01 to 8 μm average particle size,

essentially due to the crystal structure of the zeolite, for example in a range from 4 to 8 μm in the case of crystalline ones. Zeolites can also be used satisfactorily and in a range from 0.01 to 0.1 μm, for example 0.1

zen, the two or more such lattice structures with ver to 0.05 [im in amorphous products.

have different pore sizes, such as mixtures. Although crystalline synthetic zeolites are known genes of crystalline substances with one another and with amorphous 25, amorphous zeolites can also be used, which in

Zeolites. in many cases to the crystalline products or in admixture

The zeolite should preferably be superior to a monovalent cation crystalline / amorphous product. The particle

exchange zeolite, i.e. it should be an aluminum silicate with a large and pore size of such products corresponds to normal

monovalent cation, namely sodium and potassium. Usually the previously known products, but changes

it is also possible that the monovalent cation of the zeolitic molecules is possible, provided that they contain sodium as builders. have the desired properties and do not use colored text

Crystalline zeolites, which as molecular sieves according to the invention provide a white shimmer. The different types of manure that can be used at least partially are zeolites. suitable crystalline molecular sieve zeolites are described in the US

lithe A, X, Y, L, mordenite and erionite, the zeolites A patent applications 467,688 dated May 7, 1974,503,734 dated 6th

and X are preferred. It is also possible to use mixtures of such molecular sieve zeolites from September 35, 1974 and 640 793 and 640 794 from December 15, especially when described in 1975. Other such connections are in the

Zeolite A is present. These crystalline zeolites are known from US patent applications 359,293 dated May 11, 1973 and are known and described in particular by Donald W. Breck in Zeolites Mo-450 266 dated March 5, 1974. Other suitable Molecular Sieves », 1974. Commercial zeolites such as molecular sieves are found in DT-OS 2 412 837 and 2 412 839 and ser type in Table 9.6 on pages 747 to 749 40 in Austrian patent applications A 4484/73, A

mentioned. 4642/73, A 4666/73, A 4717/73, A 4750/73, A 4767/73, A

Synthetic Zeo- 4787/73, A 4788/73, A 4816/73 and A 4888/73 are preferably described in more detail according to the invention.

lithe, especially type A, or similar structures as written.

they are mentioned on page 133 of this reference. The production of amorphous and mixed amorphous / crystalline good results are obtained, for example, with a 4A molecule of 45 aluminum silicate with ion exchange properties in larsieb zeolite, in which the monovalent cation Na of the US patent application dated July 12, 1974 by Burton H trium and the pore size of the zeolite is about 4 Â; such Gedge, III and Bryan L. Madison described in more detail. Washing zeolitic molecular sieves are described in US Pat. No. 2,882,243 as medium mixtures containing such amorphous mate zeolites A. Materials are described in a patent application by John Michael Corkill Molecular Sieve Zeolites can be described in either Dehydrated 50 and Bryan L. Madison dated July 18, 1974, in ter or calcined form, containing about 0 to 1.5 detergent mixtures mixed amorphous / or up to 3% moisture in a hydrated form or containing water-crystalline aluminum silicate builders in a form loaded with this application, which additional water is described in a July 12, 1974. Preferred ion exchange amounts of 4 to 36% of the total weight of the zeolite per zeolite are amorphous zeolites according to the Belgian patent specification of the same type. The water-containing hydrated 55 835 351 of the general formula molecular sieves are preferred according to the invention if such crystalline products are used. Manufacturing M20 • A1203 • (Si02) z • wHzO,

such crystals are known. For example, in such a production of the zeolites A, the hydrated zeolites in the z are from 2.0 to 3.8 and w are from 2.5 to lith crystals which are formed in the crystallization medium, 60 6, where M especially sodium. The agglomeration

such as, for example, water-containing amorphous sodium aluminum sintering or connecting the finely divided zeolite framework

Likatgele used without high-temperature drainage, water-soluble binders used substance particles must i.e. without calcining to a water content of 3% the particles in the dry or nearly dry state of or less, as is normally the case in the manufacture of such - for example a free moisture content of less than small crystals for the use of catalysts, e.g. Crackkata- 65 5% without taking into account the lysator held by the zeolite. The crystalline zeolites can hold water or water of hydration firmly together, but should dissolve quickly in their either fully hydrated or partially hydrated and then release the particles.

formated by filtering off the crystals from the crystal if the agglomerates with water, such as

5 636124

Wash liquor, come into contact. After cold water, this effect is said to result in viscous mucus solutions, which generally form an appropriate storage and storage temperature of no gel, even though they are usually obtained synthetically

- 20 to 40 ° C and can also be used at washing temperatures in the range of 10 gel-forming gums,

occur up to 80 ° C. The binders that can be used are, for example. for example gumra

wise water-soluble crystalline or non-crystalline substances, the 5 dikum, ghatti, karayagum and tragacanth as well as other plants

meet these conditions and agglomerate particles such as guar, linseed oil and locust bean gums and during normal handling, e.g. when filling and mucilage, as well as those of Tang such as agar, algin and during transport, and still keep a quick carrageenin and also gum-like polysaccharides from He-

Dissolution of the binder and a dispersion of the finely micellulosic or polyhydrocarbons with a high divided molecular sieve zeolite particles on contact with water or pentosan content. Particularly suitable synthetic gums are to be favored or brought about. The dissolution rate must be carboxymethyl cellulose such as sodium carboxymethyl cellulose,

Be dimensioned so that the molecular sieve zeolites quickly prevent dirt deposits on detergents like it does

Can eliminate calcium hardness. The dissolution rate even with hydroxypropyl, methyl, ethyl, hydroxymethylpro

of the binder and the dispersion of the zeolite particles can be pyl and hydroxyethyl cellulose.

by improving the fact that the agglomerates and / or other suitable binders include, for example, sugar or a foaming material in the mixture, such as sucrose and mostly syrup and various pentoses, and that the agglomerate particles are broken up by the de-glucose. Suitable polymeric products with the inherent binding of air bubbles are favored and the dissolving and shading are accelerated, for example, by water-soluble polymers such as poly-dispersing of the individual components. From nylpyrrolidone, polyvinyl alcohol, optionally together with this reason, one can use sodium carbonate or preferably 20 polyvinyl acetate, which likewise prevent dirt build-up in the sodium hydrogen carbonate with the mixture of zeolite and wash liquor. Furthermore, polyacrylamides can also be combined as binders, while the rest of the detergent can be used alone or together with other polymers. Citric acid, monosodium phosphate, boric acid or other All non-ionic acidic components can be used as non-ionic surfactants, which are preferably encapsulated or surface-active substances, such as those agglomerated with the bicarbonates, and then, if necessary, Detergents and Emulsifiers », 1973 by McCutcheon to produce carbon dioxide. and in Surface Active Agents, Volume II by Schwartz, Perry and binders are water-soluble starches, gum, sugar, Berch are described. These non-ionic surfactants are used in polymers and non-ionic surfactants and their mixtures. Room temperature, usually pasty or waxy starch binders, are preferred because of their good combination of solids, which either dissolve quickly enough in water with good binding properties and rapid dispersing properties or at a wash liquor temperature of more than 40 ° C. The starch is usually in particles or granules that melt quickly. Non-ionic liquids with a diameter of 2 to 150 [im in front; liquid at room temperature; most surfactants are less suitable because they contain 22 to 26% amylose and 74 to 28% to sticky agglomerated starches. merate with poor flow properties that can clump together with La-70% amylopectin, albeit other types of starch. Suitable non-ionic ten-type corn starch that is amylose free. Starch is understood to be the various 35 polyalkenoxy derivatives with lower alkene residues, the most diverse types of starch, such as natural starch usually by condensation of alkylene oxide, e.g. Ethylene including corn starch, potato starch, tapioca, cassava oxide or propylene oxide can be obtained with a compound, or other starch types from bulbous plants and amylo- which have a hydrophobic hydrocarbon chain and one or more and / or amylopectin; furthermore, hydroxyalkyl starches may have higher active hydrogen atoms, such as higher alkyl radicals such as hydroxyethyl starch, hydroxylated 40 higher alkyl phenols, higher fatty acids, higher fatty acid starches and starch esters such as starch glycolates and captans, higher fatty amines and higher fatty polyols and other starch derivatives with similar properties , as with alcohol, such as, for example, with fatty alcohols with 8 to 20 or, for example, partially hydrolyzed starch and analogously also deri 10 or 18 carbon atoms in the alkyl chain, which are through the main components of amylose and amylopectin, on average with 3 to 30 and preferably 6 to 20 lower are used. Corresponding cellulose compounds and 45 alkylene oxide units is alkoxylated. Preferred non-ionic derivatives of which belong to the rubbers, while the corresponding surfactants have the general formula R0 (C2H40) nH, in which radical carbohydrates such as sugar and their hydrolysis pro- a linear saturated primary alcohol radical or an alkyl radical products from another class that can be used according to the invention with 12 to 18 carbon atoms and n is an integer of 6 ren binders. up to 20. Suitable commercially available, non-ionic surfactants are

Starch varieties are particularly suitable because they produce a creamy, for example 50, ethoxylation products with an average of eleven adhesive, aqueous solutions, and because the agglomerated ethylene oxide units and a fatty alcohol chain with 14 to 15th particles after drying or after sorption of the carbon atoms or C12 to C15 Fatty alcohols that are ethoxylated with moist parts from the starch solution by the zeolite in an average of 7 ethylene oxide units (neo-corresponding small particles can be broken down dol) as well as C16 to Clg alkanols, which with an average of 10 to or as the agglomeration to the desired particle size Ethylene oxide units are ethoxylated (Alfonic) and Ige-se is controllable or the detergent pal types of approximately the same size. Instead of the non-ionic surfactants, particles can also be adapted. Starch is shown in whole or in part for the agglomeration of amphoteric or anionic surfactants and can serve as a continuous phase that is set.

Encloses zeolite particles in the desired small size. Instead of individual binders, binder can also swell while the starch swells on contact with water and the mixture can be used, which is particularly desirable if the manure between the agglomerated particles is weakened additional detergent component such that these particles are rapidly dispersed in the non-ionic surfactant by the circulated water, a means of preventing the washing water. Another advantage of starch- dirt deposits such as starch or sodium carboxymethylcel-ke is that it does not affect the product and contributes to lulose and additional builders such as STPP or Na2C03 do not contaminate the waste water. 65 holds. In these cases, the presence of the gums and the associated sticky substances together with the insoluble molecular sieve zeolites usually promote high-molecular polyhydrocarbons natural particles a quick dissolution of the product, because of the other or synthetic origin; Most of the non-ionic surfactants can be used to promote wetting,

636 124

The addition of calcium salts and the prevention of redeposition of dirt by sodium carboxymethyl cellulose or the corresponding gums occurs before the main part of the detergent has completely dissolved, namely the other components, such as the usual synthetic organic surfactants and soluble builders or filler salts. Of course, sodium carboxymethyl cellulose or starch can also be incorporated in the other portion of the detergent mixture, as can also be the case for zeolite builders, additional builders, non-ionic surfactants and other additives which are used to balance the properties of the detergent. To balance the properties of the individual constituents, the usual detergent constituents can also be agglomerated together with the zeolites.

The water-soluble, synthetic, organic detergents can be anionic, non-ionic, cationic and amphoteric surfactants in the detergents according to the invention, although cationic surfactants are generally not used. Ampholytic and amphoteric surfactants are generally not as effective as anionic and non-ionic surfactants, so that anionic surfactants and non-ionic surfactants or their mixtures are best present in the separately spray-dried detergent portions of the detergents according to the invention.

Suitable anionic surfactants are, for example, higher alkylbenzenesulfonates having 8 to 20, preferably 12 to 18 and in particular 10 to 16 carbon atoms, the alkyl radical preferably being linear. Compounds having 11 to 13 or 14 carbon atoms in the alkyl chain are preferred.

Alkylbenzenesulfonates with a higher content of phenyl isomers in the 3-position or in a higher position and a correspondingly lower are particularly preferred. Content of phenyl isomers in the 2- or 1-position, so that the benzene ring is preferably mainly substituted in a 3-position or in a higher position; such surfactants are described, for example, in US Pat. No. 3,320,174. However, terminally alkylated LAS detergents can also be used.

Other suitable anionic surfactants are, for example, olefin sulfonates, which are generally long-chain alkenylsulfonates or long-chain hydroxyalkanesulfonates, the OH radical being found on a carbon atom which is not bonded directly to the carbon atom with the SO 3 group. The olefin sulfonates usually contain mixtures of these two types of compounds, usually together with long-chain disulfonates or sulfate sulfonates. Such olefin sulfonates are described, for example, in U.S. Patent 2,061,618.3,409,637.3,332,880, 3,420,875.3,428,654.3,506,580 and British Patent 1,139,158 and in Fat Soap Paints, Volume 72, No. 4, pages 247 to 253 (1970). These olefin sulfonates can be straight chain a-olefins, internal olefins and olefins, the unsaturation of which is formed by a vinylidene side chain, e.g. Dimers of a-olefins are made from their mixtures, with a-olefins usually being the major ingredient. The sulfonation takes place with sulfur trioxide under a low partial pressure, in which, for example, the S03 is strongly diluted with inert gas such as air or nitrogen or is used under vacuum. This reaction generally leads to alkenyl sulfonic acids, optionally together with sulfones. The acidic product obtained is then usually treated with alkalis and converted into hydroxyalkanesulfonates and alkenylsulfonates with ring opening. The olefins usually contain 10 to 25 and in particular 12 to 20 carbon atoms and form a mixture of C12, C14 and C16 olefins.

Other water-soluble anionic surfactants are, for example, higher paraffin sulfonates with 10 to 20 carbon atoms, such as primary paraffin sulfonates, which can be obtained by reacting long-chain a-ole-fine and bisulfite, e.g. Sodium bisulfite or paraffin sulfonates, the sulfonate residues of which are distributed along the paraffinic chain. The products can be produced by reacting 5 long-chain paraffins with sulfur dioxide and oxygen under UV light and then neutralizing with NaOH or other bases; e.g. according to US-PS-2 503 280.2 507 088.3 260 741.3 372 188 and DT-PS-735 096. The hydrocarbon substituent of the paraffin sulfonate preferably contains 13 to 17 carbon atoms and is usually a monosulfonate and optionally a di, tri or higher sulfonate. Paraffin disulfonates can be used, for example, as a mixture with the corresponding monosulfonate, for example as a mixture containing up to 15-30% of the disulfonate.

The hydrocarbon substituent of the paraffin sulfonates is generally linear, but branched paraffin sulfonates can also be used; the sulfonate residue can be terminal or on the second carbon atom or on another 20 carbon atom of the chain. In these sulfonates or higher sulfonates, the sulfonate residue can be substituted along the chain at different carbon atoms.

Other anionic surfactants are, for example, soaps or water-soluble salts of higher fatty carboxylic acids, such as lauric acid 25 re, myristic acid, stearic acid, oleic acid, elaidic acid, isostearic acid, palmitic acid, undecylenic acid, tridecylenic acid, pentadecylenic acid and higher alkanoic acids substituted in the 2-position with lower alkyl radicals such as -tridecanoic acid, -pen-tadecanoic acid or -heptadecanoic acid and other saturated or 30 unsaturated fatty acids having 10 to 20 and preferably 12 to 18 carbon atoms. Soaps of dicarboxylic acids, such as dimerized linoleic acid, can also be used, or soaps of other higher molecular acids such as resin acids or tall oil acids, such as abietic acid; A soap mixture of tallow fatty acids and coconut oil fatty acids, e.g. in a ratio of 85:15.

Other anionic surfactants are, for example, sulfates of higher alcohols such as sodium lauryl sulfate, sodium tallow alcohol sulfate, sulfated oils or sulfates of mono- and diglycerides of higher fatty acids, such as stearic acid, monoglyceride, monosulfate, higher alkyl poly (lower alkenoxy) ether sulfates, such as sulfates Condensation products of lower C2 to C4 alkylene oxides, such as ethylene oxide and a higher aliphatic alcohol, such as, for example, lauryl alcohol with a molar ratio of alkylene oxide to alcohol of 1: 1 to 5: 1 or 30: 1; Lauryl or higher alkyl glycerin ether sulfonates and aromatic poly (lower) alkenoxy ether sulfates such as sulfates of the condensation products of ethylene oxide and nonylphenol with 1 to 20 and preferably 50 to 2 to 12 ethylene oxide residues per molecule. The ether sulfates may also contain a Q to C4 alkoxy group on a carbon atom near the sulfate group, such as a monomethyl ether monosulfate of a long chain vicinal glycol, e.g. a mixture of vicinal alkane diols with 16 or 5S17 to 18 or 20 carbon atoms in the straight chain.

Other water-soluble, anionic surfactants are, for example, higher acyl sarcosinates such as sodium lauryl sarcosinate and acyl esters, e.g. Oleic acid esters of isethio-nates and acyl-N-methyl taurides, such as, for example, potassium N-60 methyl lauroyl or oleoyl taurides. Other suitable anionic surfactants are, for example, higher alkylphenol sulfonates, such as, for example, alkylphenol disulfonates with C12 to C25 alkyl radicals, preferably linear alkyl radicals with 16 to 22 carbon atoms, which are obtained by sulfonating the corresponding 65 alkylphenols and in excess 1.6 and preferably more than 1 Contain 8 S03H residues per alkylphenol molecule. The disulfonates can e.g. possess phenolic hydroxyl residues blocked by etherification or esterification.

7 636 124

The hydrogen atom of the phenolic OH group can be replaced by an alkyl, e.g. by ethyl or hydroxyalkoxyalkyl, e.g. the mixture of silicates or carbonates can be replaced alone or in Mi-a - (CH2CH20) xH, in which x is greater than 1, e.g. included. In addition to the inorganic builders-3,6 or 10, the alcoholic OH group obtained, organic builder salts can be used, such as Al e.g. to form a sulfate, e.g. -0S02Na is esterified. 5 potassium salts of nitrilotriacetic acid, citric acid, 2-hydroxy

Although the above-mentioned organic carboxylates, ethyleniminodicarboxylic acid, borglucoheptanoic acid, polycarbon sulfates and sulfonates are preferred, the diacids such as, for example, polymaleates with a lower speaking organic phosphate and phosphonate than anio-molecular weight below 1000, for example of 400,600 or niche surfactants, can also be used be used. 800, as well as polyphosphonic acids and especially alkali salts

In general, the anionic surfactants are alkali salts such as all of these compounds. Suitable carriers are also potassium salts and especially sodium salts, although also, for example, alkali, in particular sodium sulfates, bisulfates, ammonium cations and substituted ammonium cations of and chlorides as well as fillers and organic fillers and C2 to C4 alkanolamines, e.g. Triethanolamine, triprop solubility enhancers such as urine anolamine, diethanol monopropanolamine, and Q to C4 alkyl.

amines, e.g. Methylamine, ethylamine, secondary butylamine, diis. The detergents according to the invention consist once of the components which are likewise agglomerated, namely the molecular sieve, which consist of methylamine, tripropylamine and triisopropylamine. Zeolites and the binder, and secondly from the com-

Alkali salts of sulfated and sulfonated oleofine complementary components, namely the separately sprayed compounds, are preferred over carboxyl-, phosphoric acid- dried particles which are a detergent substance and filler and phosphonic acid compounds. 20 substances and / or builders as well as usual other additives

Non-ionic surfactants can be used with the added or included components that are usually used to complement the spray drying approach and are often present, with the exception of the heat-sensitive additives, in relatively small amounts in the mixed batch as a batch or such additives that the Flow properties of the product are present when it is spray dried. improve it. Such additives include for example

The amphoteric surfactants are generally higher fat carcinols such as sodium perborate, coloring substances such as boxylates, phosphates, sulfates or sulfonates, which contain a cationic example of pigments, dyes and optical brighteners.

see substituents such as an amino group containing foam stabilizers such as alkanolamides, e.g. Laurin myristine, for example, is quaternized with a lower alkyl radical or acid diethanolamides; Enzymes, such as proteases, have an extended chain on the amino residue by condensation with agents to protect the skin, such as water-soluble proteins with a lower alkylene oxide, e.g. an ethylene oxide, 30 molecular weight, which is by hydrolysis of protein-containing. In some cases, the amino residue can be a heteroeyelike material such as animal hair, skins, gelatin and Colla ring. Commercially available products can be obtained, for example, gene, these products also being binders sodium N-coconut-β-aminopropionate (deriphat 151) and which can be used; Foam pressers such as silicones, anhydrous form of a heterocyclic diaminodicarboxylic acid, plasticizers such as ethoxylated lanolin, bactericides

35 such as hexachlorophene, opacifiers such as polystyrene suspensions or behenic acid, buffer substances such as alkali borates, acetates, bisulfates, perfumes and agents for improving the flow behavior such as ground clay.

The proportions of finely divided zeolite builder particles 40 with ion exchange properties and water-soluble binder in the agglomerates are usually in a range from 10:90 to 90:10, preferably from 20:80 to 80:20 and in particular in a range from 30:70 to 70:30. It is generally expedient if the agglomerates are no further cationic surfactants, for example quaternary amines contain 45 components, with the exception of smaller proportions of with a water-soluble anion such as an acetate, sulfate or additives such as perfume and agents for improving the flow chloride, where suitable quaternary ammonium salts of behavior; However, these should not make up more than 5% of the agglomeration-higher primary fatty amines by condensation with a rat particle. In some cases, however, 10 lower alkylene oxides can also be derived, such as ethylene oxide or 20% other additives, especially if condensation products of N-tallow trimethylene diamine (etho-50 these agglomerates are used in bleaching detergents) and polyethoxylated quaternary ammonium chlorine and that Bleach is heat sensitive and therefore rid (Ethoquad); Furthermore, quaternary ammonium salts of hetero-sequence cannot be dried with the other complementary particles of spray-cyclic aromatic amines such as N- (laurylcoloaminofor. Thus, up to 50% of perboromethylmethylmethyl) pyridinium chloride (Emcol) and also higher fats, Percarbonates or peroxymonosulfates the agglomera-amine oxides such as bis (2-hydroxyethyl) octadecylamine oxide 55 th be present. Without such additives, the Ag-

(Aromox). glomerates only from the two components, namely zeolites

As a carrier for the synthetic organic detergents and binders, free moisture present and especially for the anionic surfactants is generally taken into account. However, the weight of the filler used, such as water-soluble silicates, water of hydration of the zeolites, the water which is obtained from the Zeo e.g. Alkali silicates with a molar ratio of metal oxide to lith particles and / or the binder is bound. So that the product is not sticky or flows poorly, the Si02 is of the order of 1: 1 or 1: 1.5 to 1: 3.2, and is preferably 1: 2.0 to 1: 2.5, for example with a percentage of free moisture to 10%, especially less than 5%

Na20: Si02 ratio of 1: 2.4, as well as alkali polyphosphates and in some cases limited to no more than 3%, such as pentasodium tripolyphosphate and tetrasodium pyrophos- 65 The other component or the complementary component, as well as borates such as borax and alkali carbonates such as Na component of the detergent, namely the spray-dried other

triumearbonate and sodium bicarbonate. These salts can contain particles of the detergent, usually contain synthetic as hydrated products, but also as anhydrides. see, organic, detergent substance including soap,

the general formula that is sold as "Miranols".

636124 8

preferably anionic surfactants, washing alkalis, builders. Particle size is generally only required for the finely divided and / or fillers and other conventional additives. Usually zeolite builder particles with the water-soluble binders will mix the heat-resistant additives into the spray-drying agent particles in such a way that the divided particles are aggregated so that they form uniform, free-flowing particles. The binder particles or the zeolite particles with good flow properties and good appearance can be moistened beforehand or in some other way with a ben. Although spray drying is preferred for the production of these complementary particles, preferably an aqueous solvent, these other parts, in particular water, can be moistened so that the binder can also be produced by other processes, in which the zeolite particles adhere and hold them together. Preferably by spray cooling, by drying in the manner, the particles of both components are drum together, by drying in the trough, by drying in air 10, and together with a fine jet of water or and by drying by hydrating anhydrous compo with steam on the the moving surfaces of these elements of a fluid mixture. If these various particles are aimed to ensure that binder or oversize particles or chunks are adequately prepared, they can be moistened and partially dissolved on the surfaces so that they are crushed to the desired size, while adhering to a plurality of zeolite particles favored too small particles can be reprocessed. 15 will. By appropriately adjusting the mixing speed, these other or complementary parts of the temperature and the proportion of water or other particles or spheres contain 5 to 40, preferably 10 to 25% by weight of solvent, the extent of the adhesion can correspond to the wash-active substance, 10 influences to 60 and preferably 15 to 40 and the particle size, which is achieved within a certain wt .-% washing alkalis or builders and 10 to 80 and time are controlled. In the case of a preferred preferably 20 to 60% by weight of fillers and further 1 to 20 20% of the embodiment according to the invention, the nonionic and preferably 2 to 10% by weight of additives which are in the surface-active condensation products of the above are no longer described Make up as 5% and preferably 2% of the same type, starch, sodium carboxymethyl cellulose, polyvinyl free-flowing complementary component. alcohol, polyvinylpyrrolidone and / or polyacrylamide with the

The proportion of agglomerate particles to the other complex- very fine zeolite particles in the presence of moisture, with -mentary particles can be adjusted, for example, from 2 to 30% of original free moisture, depending on the desired properties, but is generally in a circulated manner Obtain particles of the desired size; range from 1:10 to 5: 1 and preferably in a range of these particles can further be classified or sieved-1: 10 to 4: 1 and in particular in a range of 1: 5 to 3: 1. to remove oversized or too small particles. The composition of the final detergent can be described in terms of circulation, especially when using a water based on a total composition, 30 anhydrous or only partially hydrated zeolites or because it is mixed by mixing the agglomerate particles and the other when using a hydratable salt as a binder ren separate complementary particles can be obtained. In which the free moisture is removed and the product in a large finished detergent of this type, the content of this amount in the form of a loosely held mass of detergent active substance is usually 5 to 35 and preferably 5, which will then be broken down to the desired particle size. to 25 and in particular 10 to 25% by weight, the 35 content being reduced. Alternatively, the molecular sieve and builder salts, with the exception of the zeolites 10 to 60, and the binder can be solidified in water and, when the mixture has ended, is preferably 15 to 40% by weight and the content of the filler in this product is dried and, if appropriate, to the desired amount - Break up and crush the substance salts in a range from 10 or 15 to 60 and the preferred size. The various amounts are 20 to 40% by weight, while the content of zeolite particles can then be ground in a rolling mill for removal with ion exchange properties to be about 5 to 50, preferably 40 sharp edges, oversized portions 5 to 40 and in particular 10 to 30 wt .-% and the le reduced to the desired size and too small proportions of the binder, which can also be reprocessed as a means of preventing. According to another erfin dirt deposit, in a range from 0.5 to 20 and the embodiment according to the invention, molecular sieve and preferably 1 to 15 and in particular 5 to 10 wt. Binders with each other in a suitable for agglomeration-Accordingly, the preferred phosphate-free washing mit-45 neten state can be mixed, whereupon the agglomerates in tel 5 to 25% higher linear alkylbenzenesulfonates with C12 to suitable dryers such as tumble dryers, film dryers C18 alkyl residues, about 5 to 20 % By weight of sodium silicate are dried with egg and tunnel dryers before they are classified into their desired Na20: SiO2 ratio in the range from 1: 1 to 1: 3.2 and desired size. When agglomerating about 15 to 60 wt .-% sodium sulfate and 5 to 40 wt .-%, the desired additives such as perfume, dyes, pigments and a zeolite with ion exchange properties and about 0.5 50 of the like can be added so that the agglomerated parts bis 20% by weight of starch or non-ionic, wash-active binchen contain the desired aroma or the desired appearance, these portions being preferred for obtaining or optionally colored differently from the other composition in a range from 8 to 15 or 5 to 15 detergent particles, namely the complementary particles which are or 20 to 50 or 10 to 30 or 2 to 10% by weight, but can also have the same appearance. The agglomerated wash-active substance, a linear sodium alkylbenzenesulfonate particle, can also be prepared by using it nat with a C12 to C15 alkyl group. Checks such, for example by changing a dissolved or a composition, by melting non-ionic detergent to a moving one, by spraying on part or all of the sodium silicate by Na bed of the zeolite particles. The common sprayed trium carbonate is replaced if washing and spray drying which are completely phosphate-free is generally also possible, is to be produced in a medium way or by pentasodium tripolyphosphate 60. The zeolite particles can agglomerate from the start or other suitable polyphosphates if the presence of, i.e. have a larger particle size than the final phosphates possible. Furthermore, a further fraction of particle size can be used, before mixing with the 5 to 40 and preferably 10 to 25% by weight of such binders or with a binder mixture to agglomerate the other components in the production of, for example, a, phosphate Non-ionic surfactant and phosphate detergent are added, the proportions 65 being a water-containing silicate builder or with additional sodium silicate and sodium carbonate, for example on the tripolyphosphate or both.

Reduce half. The other particles or complementary particles of the

To produce the agglomerate particles in the desired detergent, preferably in the usual manner

636 124

Spray drying obtained by a batch containing 40 to 70 wt .-% solids in an aqueous medium through a narrow opening, for example 0.5 to 2 mm in diameter at a temperature of 50 to 140 ° C, at a pressure of 7 to 56 kp / cm2 sprayed into a drying gas at a temperature of 200 to 500 ° C to obtain spherical particles with a moisture content of about 2 to 12%. These particles are classified to the desired particle size and then mixed with the agglomerate particles, for example in a drum mixer, after which the end product is obtained. The other particles or complementary particles can also be produced in other known ways, for example by drum drying or by dry mixing.

The processes for producing the agglomerated particles and those for producing the spray-dried complementary particles are known per se, can be carried out commercially and without difficulty. The products obtained are free-flowing, but may also contain additives which improve the flowability or flowability, such as clays or other additives which are added during or after mixing. The end products can be used in the usual way, namely as household and industrial detergents. They do not separate during storage or shipping; they have an excellent cleaning effect without the textiles showing a white shimmer or white spots due to zeolite deposits.

The advantage of the products according to the invention, namely both the agglomerates of zeolite with ion exchange properties and binders and the end products containing such zeolite builders, is obtained if both crystalline and amorphous zeolites of the types described are used, amorphous zeolites being preferred in many cases will. Even partially hydrated or fully hydrated amorphous products, despite their low bulk density of, for example, 0.3 g / ml compared to a bulk density of 0.6 g / ml in the case of commercially available crystalline molecular sieve zeolite A, can form free-flowing builders with bulk densities in the range of 0 , 3 to 0.8 and for example from 0.5 to 0.8 and even higher. In addition, the builder beads and the detergents containing these builder particles are dust-free despite the lower final particle size of the amorphous material, especially since the size of the aggregate material is approximately the same. The absorption capacity for the binder, for example nonionic surfactants, is much better in the case of amorphous zeolites, since the nonionic surfactant in its liquid waxy or greasy form is believed to be amorphous, both in an aqueous medium and in a molten or otherwise obtained fluid state Sufficiently penetrates particles per se or in their aggregate form without the surface of the particles becoming too sticky, although the zeolite particles agglomerate to the desired particle size. Accordingly, the finished detergent scaffold beads or the detergent beads can contain substantial proportions of non-ionic surfactants of, for example, 5 to 40 and preferably 5 to 25% by weight. Until now, it was believed that such large amounts of detergent pellets were not permitted due to the stickiness and poor flow properties. The amorphous zeolites convert the liquid waxy or sticky surfactants, such as non-ionic surfactants, very effectively into free-flowing solid individual particles, and surprisingly even hydrated amorphous zeolites are much better in this regard than anhydrous crystalline zeolites. The result of this is that larger amounts of non-ionic surfactants can be present in the detergents, and a better washing effect is achieved, and because of the smaller final size of the amorphous zeolites, a less objectionable white coloration of dark-colored laundry occurs. In addition, the amorphous zeolites have better exchange properties for magnesium ions than the corresponding crystalline products, which is important wherever magnesium hardness occurs.

The amorphous zeolites and the anionic surfactants can be mixed in various ways, such as, for example, the above-described mixing processes for detergent and zeolites; however, the easiest way to mix the two io products is to circulate them until the product is sufficiently agglomerated and the surfactant binder is sufficiently absorbed. Instead of using only the surfactant as a binder, mixing can also take place with other binders present.

15

In a further embodiment according to the invention, a slurry of an anionic surfactant with a solids content of 40 to 70% by weight, for example a 60% aqueous slurry of linear sodium tride-20 cylbenzenesulfonate with a content of about 8% sodium sulfate and other impurities, can be mixed with the equal amount of an amorphous zeolite, e.g. according to Belgian patent specification 835 351. The zeolites generally have a BET surface area of about 50 to 150 m 2 / g, a final particle size of 0.03 to 0.06 μm and an aggregate particle size of 0.2 to 10 μm, with most aggregates in a size range from 3 to 5 [in, a density of 2.1 g / ml, a bulk density of 0.3 g / ml, a moisture content of about 2.5 to 6 moles of H20 per mole, a Na20 / Al203 / Si02-30 molar ratio of 1: 1: 2.1 to 2.6, a calcium exchange capacity of 260 to 350 mg CaC03 / g and a hardness reduction rate to the residual hardness (in mg CaC03 4.5 1 each) from 0.07 to 0 , 15 in 1 minute and less than 0.035 in 10 minutes. Mixing both components in the same weight amounts is a free-flowing and free-flowing product, which does not work with short mixing times of e.g. Dust for 1 to 5 minutes. Despite the essentially hydrated state of the amorphous zeolites with a content of about 20% moisture and the presence of a noticeable amount of moisture in the anionic detergent, the cleaning agent is free-flowing without further drying measures. The end products can have a sufficiently high density, but products with a lower density can also be produced in various ways, for example by adding a gas to the material to be agglomerated, hammering it in or adding a bubbling component.

According to the invention, such a zeolite with ion exchange properties, which already contains a moisture content of up to 30% and usually up to 25% or more 50, can be mixed with various other detergent components to form a free-flowing particulate material from such a mixture of others Obtain detergent components even if some of these components are liquid, this being possible without the use of heating or drying equipment. As a result, the end product will usually be much more readily soluble in the wash water and therefore more effective in washing, since the various components can develop their effectiveness very quickly after addition to the wash water, because the individual particles break up very quickly.

In the following, the invention will be described with the aid of examples, all quantities being based on weight, unless stated otherwise.

65

example 1

The same was used to produce a readily disintegrable, insoluble detergent builder in agglomerate form with a particle size corresponding to 8 to 100 meshes

636124

10th

Amounts of potato starch and a molecular sieve zeolite 4A with the moisture content in products A, B and C were

a final particle size of 2 to 10 [in the formula de compared to that of Example 1 increased and decreased by 50% and in product D not more than 10%. The Na12 (A102 • Si02) i2 • 27H20, agglomerates obtained showed the same good properties as pro-

5 products according to example 1.

used in a fully hydrated state.

The potato starch was used in the same amounts of water as example 3

dissolved or well dispersed and then with the hydrated in an inclined tube mixer that was rotating at 30 rpm,

Zeolites mixed, with the hydrated zeolite at 20%, the following mixtures were each further mixed in the presence of moisture, for example 25% moisture content of 10% water sprayed on, with hydration being carried out within. Excess moisture was sufficient for 5 to 10 minutes of agglomeration of the mixing and further heating in a pan and good free-flowing non-sticky products were used to get dryers up to a moisture content of about 8%, which were used as builders for heavy duty detergents suitable wa-distant. The agglomerated particles were then passed through a sieve and the laundry was not discolored.

No. 8 pressed, the non-penetrating particles being broken up in a 15E): 50% zeolite 4A and a condensation product from a grinder and the fines again in higher fatty alcohol with 14 to 15 carbon atoms per mole of mixer with further strength and Zeolite particles and 11 moles of ethylene oxide (Neodol 45-11);

were processed. F): 50% zeolite X, anhydrous, 25% of the condensation pro

The zeolite agglomerates obtained were free-flowing products according to E and 25% potato starch;

dimensionally stable, dry bodies with less than 10% free 20 In the case of analogous approaches, 0.3% perfume and 0.8% op-moisture, which almost sonic brighteners were used instead of 1.1% zeolite when introduced into washing water, were continued distributed. A disintegration to zeolite particles with a final size of 2 to 8.3 μm is achieved approximately within one minute of example 4 when the agglomerates are added to the washing water while stirring added 25 modified with regard to the zeolite content, so that under de-ent; Such a dispersion is obtained within 2 minutes by proportionally setting the other constituents at low temperatures of about 10 ° C. When the products contained 30%, 50% and 70% zeolites. This zeolite builder agglomerate was obtained with corresponding, good, good builder agglomerates, which were suitable for coarse-washing, complementary, particulate detergent particles with an agent and, after drying on a line, are used for the content of builders and fillers, and 30 washed textiles didn't leave a white shimmer. a washing liquor which is quick and extremely effective if, as zeolites, mixtures of zeolites, e.g. Mixtures washing effect developed, because the zeolite is immediately available for a Cal from equal proportions of zeolite 4A and zeolite X, and that was-cium exchange. The insoluble zeolite fraction free, partially hydrated or fully hydrated are in such a small form that they are not used in between, you also get suitable skeleton spaces of the textiles, regardless of the fact Agglomerates. If instead of the zeolites 4A and / or whether the laundry is hung up to dry or zeolites X or other zeolites including zeolites Y and L are machine-dried. can be used, such as those mentioned in the

According to another process, the zeolite particles were described in Austrian, German and US patents and the starch particles were circulated with one another in a mixer, good products are also obtained, the calcium and then with 8% water, based on the total water in the wash water remove faster and less zeolitic weight of the mixture, sprayed, whereby the circulating builders left on the laundry compared to Pro

Particles into larger agglomerates of almost uniform products that have been spray-dried uniformly.

Convert size in the range of 4 to 180 stitches and then a size corresponding to 8 to 100 stitches - example 5

were settled. These particles gave a free flowing 45. It became a spray dried detergent with a powder caking powder. With a further production size of 8 to 100 stitches, one procedure being carried out as before, but the particle formation of the following constituents with a solids content was not sieved after agglomeration, but the aggio of 65% at one temperature of 70 ° C. under a pressure generation was interrupted when the particles in the 28 kp / cm 2 through nozzles of about 1 mm diameter were essentially in the size range 8 to 100 meshes, including a countercurrent tower with drying air of 250 ° C after being screened again. Part of this product has been sprayed. The residence time was about 5 minutes, so then with an equal amount of sodium perborate beads that the granules or detergent beads mixed a moisture of the same diameter; possess this complementary content of about 11%. The composition of the detergent additive was in spray-dried form. The detergent particle was as follows:

get a good detergent with bleaching properties, 55

which contained zeolite builders. Components parts by weight

Example 2 in%

The procedure according to Example 1 was followed,

however, the agglomerates now have the following composition-60 linear sodium tridecyl-15

had: benzenesulfonate

A): 25% corn starch and 75% of a 5% hydrated pentasodium tripolyphosphate 32 zeolite 4A; Sodium sulfate 31.8

B): 75% anhydrous zeolite X and 25% of a mixture of sodium silicate (Na20: Si02 = 1: 2.35) 7 from equal parts of polyvinylpyrrolidone and polyvinyl alcohol; 65 polyethoxylated alcohol 1

C): 85% of a 4A zeolite and 15% sodium carboxyme- (Neodol 45-11)

ethyl cellulose borax as Na2B407 • 10 H20 1

D): 50% of a 4A zeolite and 50% corn syrup. Preservative 0.01

11

636 124

Components

Sodium carboxymethyl cellulose perfume optical brightener moisture

% By weight

0.3 0.2 0.7 11

The detergent particles obtained were mixed with the various builder agglomerates according to Example 1, so that here the detergent contained about 20% zeolite. A content of 20% zeolite was preferred in the present case, although amounts of 10 and 30% zeolite could also be used. Cotton and polyester / cotton laundry, which was soiled with a test soil made of clay, carbonaceous material and oily products, was washed at temperatures of 30.50 and 70 ° C with a detergent concentration of 0.15 and 0.25% Washed water with a hardness of 150 ppm hardness (3: 2 Ca ++: Mg ++ hardness, calculated as CaC03). Good results have been achieved with automatic washing machines that can be loaded from both the side and from above. What was remarkable was the low deposition of the insoluble builders on the washed colored textiles, especially on the light blue textiles dried on a line. The products used were heavy-duty detergents containing easily disintegrating agglomerates from molecular sieves; they had excellent properties as a commercial product, were free-flowing and did not cake when stored, sequestered the ions forming the water hardness very quickly and favored cleaning without being deposited on colored textiles. The same results are obtained when using builder agglomerates according to Examples 2 to 4.

Equally good results are also achieved if the sodium alkylbenzenesulfonate is replaced by olefin sulfonates, paraffin sulfonates, ethoxylated sulfates and other anionic surfactants and if different binders or combinations of binders are used in the same or different amounts within the stated ranges.

Example 6

The procedure was analogous to Example 5, but instead of the phosphate-containing detergent mixture of the separated particles or complementary particles, a phosphate-free detergent of the following composition was used.

Components

% By weight

linear sodium dodecyl 20

benzenesulfonate

Zeolite 4A (20% hydrated) 25

Potato starch 9

Sodium carboxymethyl cellulose 1

Sodium carbonate 13

Sodium sulfate 15

Water 5

Additives (perfume, colorants, brighteners, 5 agents to improve the reaming properties,

Bactericides, stabilizers)

Sodium silicate (Na20: Si02 = 1: 2.4) 7

The zeolites, carbonates, starch and half of the carboxymethyl cellulose were in the agglomerate particles in which the other components were present in the separate complementary detergent particles.

Although the cleaning power of this detergent was not as good as that of the product according to Example 5 due to the absence of the phosphates, acceptable results were nevertheless achieved, which were considerably better than without using the zeolites 5. Changes in the composition due to the use of other zeolites and other binders and changes in the proportions of agglomerated builders and complementary particles within the stated limits still gave good detergents with excellent washing power, which showed no signs of deposits. These results confirm that phosphate-free detergents can be manufactured with sufficient washing power without the presence of insoluble molecular sieves on the textiles. The products do not split into 15 during storage and do not dust.

The detergent according to Example 6 was modified by adding 100 parts by weight of sodium perborate or by adding 30 parts by weight of sodium perborate and 0.5 part by weight of a corresponding activator for the perborate. It was 20 at higher temperatures e.g. Washed 80 ° C, whereby good washing and bleaching results were achieved even with stains that are difficult to remove, such as red wine, coffee, tea and cocoa, especially with an activated perborate detergent. Similar results were obtained when 25 equivalent amounts of percarbonate or activated peroxymonosulfates were used instead of the perborates. Another advantage of bleaching detergents was that the zeolites absorbed dyes released from colored laundry and prevented discoloration of white items of laundry 30. If the composition was changed further, capsules of sodium bicarbonate and citric acid were used instead of the perborates, these mutually reactive solids being kept separate from one another and kept dry, so that a reaction could only take place in water. These small capsules are preferably used with the agglomerated particles, but can also be mixed with the other complementary particles, provided that they are about the same particle size to avoid settling. These products show gas formation and accelerate the rapid breaking up and mixing of the detergent components. In detergents with alkaline builders, the citric acid or the other acidic component should be as close as possible to the bicarbonate particles so that CO 2 production is possible before the acid 45 is neutralized by other alkalis in the wash liquor. In the case of detergents without alkaline builders, the reactive gas-forming constituents can also be present separately in the various granules or beads, for example in the agglomerated builders and 50 in the detergent beads.

In further modifications, flakes or granules of the components were used instead of detergent granules, whereby equally good detergents were obtained which showed no deposits of the zeolite particles on the washed textiles, although the flow properties were not quite as good. Builders other than zeolites can be omitted and the anhydrous sodium sulfate in the agglomerates and / or other particles can be hydrated to keep the moisture content low.

60

Example 7

Products according to Examples 1 to 6 were produced, but an amorphous zeolite according to Belgian patent 835 351 was now used instead of the crystalline zeolites 65. In other products, only half of the crystalline zeolite was replaced by amorphous zeolite. The amorphous zeolites corresponded to the formula according to page 11 and the properties to those of pages 36 and 37 of this Belgian Pa

636 124

12

tent script. The detergents obtained had the same good detergency as the end products according to Examples 1 to 6 and were particularly effective in hard water, in particular with a high magnesium hardness. These products are drier, and the builders based on amorphous zeolites have a better flow behavior, are less sticky and yet less dusty. After washing, there is practically no deposit of insoluble zeolites on colored textiles, even when washing in cold water and drying on a line. This is probably due to the smaller particle size and the rounder configuration of the amorphous particles. In particular when using non-ionic surfactants as binders, bulk densities in a range from 0.3 to 0.8 g / ml and higher are obtained depending on the content of binder and moisture and mixing time. In some cases, additional moisture will be present due to the sorptive power of the amorphous zeolites. In particular, if the moisture content of the amorphous zeolites is below 30%, such as 10.20 or 25% and not 30%, as in the Huber zeolites mentioned, more water has to be added, namely about 1.5 times more water Production of the starch / water mixture according to Example 1 can be used, and the subsequent drying can be omitted.

The use of these modified amorphous zeolites enables the agglomerates of zeolite and binder to completely disintegrate, so that zeolite particles with a final particle size of 0.03 to 0.06 μm result, within 1 minute after the agglomerates are submerged in the hot wash water Stirring have been added.

In the alternative method according to Example 1, up to 30% and preferably 10 to 25% water can sometimes be sprayed on instead of 8% water. In further modified examples, the water content was increased to 10 to 50% because amorphous zeolites were used.

Further modifications with amorphous or mixed amorphous / crystalline ion exchange zeolites were obtained with corresponding changes in the water content equally good builders and end products.

The detergents according to Example 7 and also those according to Examples 1 to 6 containing alkaline builders such as sodium carbonate or sodium tripolyphosphate usually have a pH in the range from 9 to 11 and preferably from 9.5 to 10.5, while Builder particles without alkaline components, apart from the zeolites, have a pH in a range from 7.5 to 10 and usually from 8 to 9.5. Accordingly, the pH of the detergents is in the appropriate range in order to achieve a good washing effect and to provide suitable mild conditions in relation to the laundry and the hands during washing, the agglomerates or binders optionally having a sufficiently high pH of 7.5 to 11 and preferably 9.5 to 10.5 to facilitate washing.

15

Although amorphous mixtures are better than those with only crystalline zeolites, the superiority is particularly evident when non-ionic surfactants are used as binders. The builders 20 and the detergents containing them are excellent commercial products, essentially because amorphous and non-crystalline zeolites are used.

25 Example 8

Because of the excellent properties when using amorphous zeolites, non-dusting, non-sticky and free-flowing coarse detergents were produced, which, if desired, had a low phosphate content or were completely phosphate-free. Such products can be manufactured with a relatively high bulk density so that they can be sold in smaller packages, and they can also contain the sticky non-ionic surfactants previously regarded as unsuitable, which in relatively large proportions of e.g. 10 or 15 to 50% could not be used so far.

The following table shows 14 different compositions and their corresponding bulk density.

Composition No.

1

2nd

3rd

4th

5

6

7

8th

9

10th

11

12

13

14

Neodol 25-7

20th

20th

20th

20th

20th

20th

20th

20th

20th

Neodol 45-11

20th

20th

Sodium tridecylbenzenesulfonate

30th

30th

30th

Amorphous zeolite

20th

20th

20th

20th

20th

20th

10th

10th

10th

10th

10th

10th

10th

Na2C03

10th

10th

10th

10th

10th

NaB03 • 4H20

10th

10th

10th

10th

10th

10th

Sodium silicate (Na20: Si02 = l: 2)

10th

10th

10th

10th

10th

9

9

9

9

9

9

9

9

9

Sodium carboxymethyl cellulose

2nd

2nd

2nd

2nd

2nd

1

1

1

1

1

1

1

1

1

Na2S04

28

8th

23

8th

Crystalline 4A zeolite

20th

20th

10th

60

60

50

40

60

50

50

60

Methyl cellulose

5

NaHCOj

8th

10th

10th

10th

Hydrated silicate

9

Pentasodium tripolyphosphate

30th

Bulk density in g / ml

0.8

0.7

0.7

0.5

0.7

0.7

0.6

0.7

0.5

0.6

0.8

0.8

0.8

0.8

The sodium silicate used had a Na20 / SiO2 ratio of 1: 2.

The various ingredients were mixed together in powder form, the powder corresponding to a mesh size of 8 to 325 (US standard sieve series). The raw material for washing was adequately dispersed by thorough mixing, with this and all other waxy or sticky components, which are not in powder form, being absorbed by the amorphous zeolite or otherwise made free-flowing. All products containing non-ionic surfactants are free-flowing, non-sticky, 60 dust-free detergent powders with excellent washing properties.

To reduce dust formation, especially in detergents with anionic surfactants, the various components, with the exception of the heat-sensitive components, such as sodium perborate tetrahydrate, can be spray-dried, the heat-sensitive compounds being added later. The mixtures based on non-ionic surfactants can also contain a proportion of originally sprayed

13 636124

have dried products and then in accordance with water-soluble builder salts is generally mixed in one. In the case of a preparation with a composition range of 10 to 50 and preferably 15 to 40%. The Verzung 1 can carbonate, silicate, CMC and sodium sulfate ratio of non-ionic surfactants to amorphous zeolite is spray dried together to particles in a size in a range of 1: 3 to 3: 1 and preferably 1: 2 to 2: 1, from 4 to 180 meshes, which then with a previously s during the ratio of amorphous zeolite to water-soluble mixture of Neodol 25-7, amorphous zeolite chem builder salt up to 1.4 and preferably in a range and sodium perborate tetrahydrate can be mixed, it can be from 3: 1 to 1: 3. If crystalline zeolites, e.g. Neodol 25-7 is also present in quantities of 10 to 60% on the other circulating compos, so their relationship to the nenten is sprayed on. It was found that when the proportion of amorphous zeolites was 6: 1 to 1:10 and preferably the presence of sodium tridecylbenzenesulfonate in the spray 3: 1 to 1: 3. The free moisture content in the generally dried component is a better sorbent for which less than 15 and preferably less than 10 and in particular less non-ionic surfactant is obtained. For all compositions - 5%, which favors the flowability. The zeolite tongues can contain the other additives such as perfume, colorants, but contain additional water of hydration, namely geEnzymes. You can also pre-live in amounts of 20% for crystalline zeolites and 20 for spray drying or with the other components before is up to 30% for amorphous zeolites. Crystalline zeolites can be mixed in. In some cases, the proportions of components in a total of 80%, but preferably less than 60%, components can be spray dried, while other proportions or less are present.

The same component previously mixed with other substances. Similar results are obtained when the amorphous ones are mixed, in which case these different proportions are mixed into the zeolites or the amorphous / crystalline zeolites by other final product. 20 0) 3rd mentioned products are replaced and if other non-

The products have a bulk density used in a range of ionic surfactants and builders.

0.5 to 0.8 g / ml, but products with bulk densities in a range from 0.3 to 0.9 can also be obtained. According to the invention, one obtains non-dusting, it has not been found that excellent detergents which separate off the presence of nonionic surfactants with a desired proportion - increase the bulk density of the product more than if anionic size 25, the synthetic wash raw materials and zeolite Ge surfactants are used. The bulk density can contain builders with ion exchange properties which can be changed by giving more or less portions of excellent washing effect and being used over similar spray-dried material, with higher spray-dried detergents having clear advantages with amounts of the same reducing the bulk density. zen, especially with regard to the non-emerging

The above examples show that satisfactory washing or extremely low deposition of zeolite particles on medium powder with a relatively high bulk density and good colored textiles after washing and drying on the

Flow behavior and good washing properties without phosphate line. According to the invention, it will also be possible to produce an extremely suitable one if amorphous zeolites are proposed as agglomerated zeolite builders, depending on the

Builders and preferably spray-dried detergents added together with non-ionic desire are used instead of anionic surfactants. 35 can improve the flowability and the ion

Products with amorphous zeolites should be favored in terms of exchange. If the zeolites are kept separate from the magnesium exchange capacity better than those with the same proportion of detergents, it is possible to mix them appropriately.

len on crystalline zeolites; furthermore, they do not result in deposits with more or less zeolite contents, as desired, wrestling on dark-colored textiles. to manufacture and greater flexibility in manufacture

Builders salts other than the zeolites are suitably made possible. The required throughput in the spray tower, which in te but not necessary components, although silicates determine the production speed in many cases, will generally be present, in particular reduced or reduced to zero, so that larger products

because of their anti-corrosion properties. Optionally, speeds of movement may be possible. Although changes are still made to organic builders, such as the composition of the spray-dried products and steu, gluconates, trisodium carboxymethyloxysuccinates and thus modifications to the final detergents are possible

Trisodium 2-oxa-l, l, 3-propane tricarboxylate. The obtained are e.g. by changing the phosphate content from 35% STPP

Products generally have a pH ranging from 25%, 15% or 0%, and these changes by others

8 to 11 and preferably from 9.5 to 10.5, while the partial working conditions of the spray tower and modification of the mesh size ranges from 10 to 200 stitches. Despite the fineness levels of the agglomerated particles can be brought about, the particles will not dust them and are free flowing and can in some cases change the composition simply by

from a narrow-necked container, the parts of the agglomerate particles and / or the incorporated

are modified, products containing crystalline zeolite types of agglomerates. In cases where non-

lithen instead of amorphous zeolites slightly less easily ionic surfactants or anionic detergent slurries

flow, and in particular if they are still wax-like or are virtually solidified by the amorphous zeolites,

contain non-ionic surfactants. 55 detergents with builders can be produced without

The results given are generally obtained that spray drying is required at all, but if the content of nonionic surfactants in a range of amorphous zeolites in these products continue to lead to

is from 10 to 60 and preferably 20 to 40% and the content is that in the case of colored laundry there are no deposits or a white amorphous zeolite in the same range. Shares of zeolite shimmer occurs.

C.

Claims (14)

636 124 2nd PATENT CLAIMS 1. Easily disintegrating, water-insoluble detergent-builders agglomerate in particle form, characterized in that it contains 10 to 90 wt .-% of finely divided calcium ion-exchanging zeolite builders particles of the general formula (M2O) • (AljC ^ y • (Si02) z • wH20 wherein M is a metal ion selected from the group consisting of sodium and potassium, Y has a value from 0.8 to 1.2, z is from 1.5 to 3.8, and w is from 0 to 9, said particles having a particle diameter of less than 15 microns, from 90 to 10% by weight of a binder for said zeolite particles , wherein the binder is selected from the group consisting of water-soluble starches, non-ionic surfactants, various gums, sugars, synthetic organic polymers and mixtures thereof, the agglomerate particles having a sieve number of 4 to 180 meshes of the US standard Sieve row. 2. builders agglomerate according to claim 1, characterized in that it contains up to 10 wt .-% of free moisture. 3. builder agglomerate according to one of claims 1 to 2, characterized in that the agglomerated particles are substantially in a size range corresponding to 6 to 140 meshes. 4. builder agglomerate according to claim 3, characterized in that the zeolite is a crystalline, amorphous or a crystalline / amorphous zeolite which can exchange calcium ions. 5. builder agglomerate according to claim 4, characterized in that the agglomerates contain a mixture of particles with a size corresponding to 8 to 100 meshes, the particle size of the finely divided zeolite particles in a range of 0.01 to 10 (xm in diameter . 6. builder agglomerate according to claim 5, characterized in that it contains 20 to 80 wt .-% zeolite particles and 20 to 80 wt .-% binder and optionally not more than 20 wt .-% of other oil additives. 7. builder agglomerate according to claim 6, characterized in that it contains 30 to 70 wt .-% zeolite particles and 70 to 30 wt .-% water-soluble binder. 8. builders agglomerate according to claim 7, characterized in that the water-soluble binder is starch. 9. A particulate detergent composition, characterized in that it contains builders agglomerates according to claim 1 and separate detergent particles, these from 5 to 40% by weight of a water-soluble, synthetic organic detergent, from 10 to 60% by weight of a water-soluble builders salt and Contain 10 to 80 wt .-% of a water-soluble filler salt, the weight ratio of the builder agglomerates to the separate detergent particles within the range of 1:10 to 5: 1, and wherein all particles of the composition mentioned have a sieve number of 4 to 180 mesh. 10. A particulate detergent composition according to claim 9, characterized in that the separate particles contain a synthetic organic anionic detergent of the sulfated or sulfonated salt type, the builder salt being selected from the group consisting of phosphates, carbonates, silicates, nitrile triacetates and borax, and wherein the filler salt is selected from the group consisting of sulfates, bisulfates and chlorides, and wherein all particles of the composition have a sieve number of 6-140 mesh. 11. A particulate detergent composition according to claim 10, characterized in that the zeolite 5 of the particulate agglomerate is a sodium aluminosilicate selected from the group consisting of crystalline, amorphous and mixed crystalline / amorphous zeolites which are at least partially hydrated and have a particle size in the range of 0.01 to 10 microns in diameter, and that the composition contains separate detergent particles which contain a synthetic detergent selected from the group consisting of C10-Ci6-alkyl-benzenesulfonates, Qo-Qs-olefin sulfonates, C10-C20 paraffin sulfonates, C10-C20 fatty acid soaps and C10- Clg-fatty alcohol-15 polyethoxysulfates. 12. A particulate detergent composition according to claim 11, characterized in that the zeolite is a hydrated molecular sieve zeolite containing 5 to 30% by weight of moisture and the agglomerate particles 20 20 to 80 wt .-% of the finely divided zeolite builders particles and 20 to 80 wt .-% water-soluble binder and that the weight ratio of the agglomerate particles to the separate detergent particles is 1:10 to 4: 1. 13. A particulate detergent composition 25 according to claim 12, characterized in that the zeolite of the particulate agglomerate is a partially hydrated type 4A synthetic zeolite and has a moisture content of 15 to 22% by weight and a particle size of 0.2 to 10 microns in diameter the agglomerate particles contain from 20 to 30 80% by weight of finely divided molecular sieve zeolite builder particles and from 80 to 20% by weight of water-soluble starch, the separate detergent particles contain a higher linear C10_16-alkylbenzenesulfonate and sodium silicate and are spray-dried Pearl form, and the weight ratio of the agglomerate particles to the separate detergent particles is from 1: 5 to 3: 1. 14. A particulate detergent composition according to claim 12, characterized in that the agglomerate of 30 to 70 wt .-% of a particulate, partially hy- 40 drained, type 4A, synthetic zeolites with a moisture content of 15 to 22% by weight and a particle size of 4 to 8 microns in diameter, and containing 70 to 30% by weight of a water-soluble binder which is a mixture of water-soluble Starch and a condensation product 45 of a higher fatty alcohol with 10 to 18 carbon atoms and 3 to 10 moles of ethylene oxide per mole of fatty alcohol, the separate detergent particles contain a higher linear Cio_i6-alkylbenzenesulfonate and sodium silicate and are in spray-dried form, and the weight ratio 50 of the agglomerate particles to the separate detergent particles is from 1: 5 to 3: 1. 55