DE2540510A1 - COARSE DETERGENTS - Google Patents

Description

Heavy duty detergent

The invention relates to coarse detergents, in particular for washing laundry, and a method for washing soiled Textiles using the coarse detergents according to the invention and also a method for production such coarse detergents.

The phosphate-based builders usually contained in heavy-duty detergents based on synthetic detergent raw materials are known to lead to eutrophication of the water, so that efforts were made to reduce the phosphate content of such coarse detergents to reduce. In the search for ecologically suitable builders for heavy duty detergents, one has found Nxtrxlotriacetate used, which, however, are viewed as questionable in terms of their biological safety. There were also silicates and carbonates used as builders, but the latter were considered harmful, especially with regard to the risk that small children can ingest such products. In some mixtures, silicates have proven to be effective

609813/1066

but are not generally suitable substitutes for phosphates, especially with regard to washing properties. It is true that there are numerous efforts have been made to develop certain detergent compositions in order to make economically suitable combinations To obtain detergent raw material and builders or washing alkalis, their properties the coarse detergents with phosphate builders correspond, but all detergent mixtures showed considerable disadvantages in one respect or another.

The invention has set itself the task of a new, in particular To propose a coarse detergent suitable for washing textiles that does not contain any phosphates or builders of nitrilotriacetates and still has washing properties that the commercial products with a considerable Corresponding content of such builders.

Surprisingly, it was found that detergent mixtures with a certain combination of known synthetic detergent raw materials or surfactants and selected certain washing alkalis or builders behave in the same way as normal commercial detergents when washing soiled textiles with phosphate builders, whereby the dirt removal from cotton is even better with the new detergent mixtures than with the previously known coarse detergents based on phosphate.

609813/1066

According to the invention, a coarse detergent is proposed which is characterized in that it contains 8 to 20% by weight of a water-soluble paraffin sulfonate washing raw material, 4 to 12% by weight of a water-soluble olefin sulfonate washing raw material, 12 to 30% by weight of a water-soluble sodium silicate with an Na ₂ O: SiO ₂ weight ratio of 1: 1.6 to 1: 2.8 and about 5 to 20% by weight of a water-insoluble molecular sieve or a silicon dioxide with an extreme colloidal particle size or a mixture thereof, the remainder of the mixture being comprised of conventional detergent additives, Builders or fillers or salts and / or water.

In order to achieve the best results according to the invention, the relevant components are preferably used in certain proportions used. According to the invention, such coarse detergent mixtures for automatic washing machines are used and finally, according to the invention, an energy-saving method for producing such powdery Proposed detergents in which the laborious spray drying is unnecessary.

The paraffin sulfonates used in the present invention are primary Paraffin sulfonates such as salts of sulfonic acid derivatives of higher primary paraffins, the carbon atom content being the Paraffins usually in a range of 14 or 16 to 22

609813/1066

Carbon atoms, although it can generally range from 10 to 25 carbon atoms. The primary paraffin sulfonates are produced by reacting long-chain Od- olefins and bisulfites such as, for example, sodium bisulfite. Paraffin sulfonates, in which the sulfonate residue is distributed along the paraffin chain, can also be used, such as, for example, the reaction products of long-chain paraffins with sulfur dioxide and oxygen in the presence of ultraviolet light, which are then neutralized with sodium hydroxide or other suitable bases. The paraffin sulfonates, together with the olefin sulfonates, are the preferred anionic surfactants of the heavy duty detergents according to the invention. If these surfactants are used alone and not with other components of the mixture, they result in extremely sticky and unsuitable detergents; Surprisingly, however, with the present mixtures they result in suitable free-flowing and non-sticky mixtures. The hydrocarbon radical of the paraffin sulfonates preferably contains 14 to 22 and in particular 17 to 18 carbon atoms. The paraffin sulfonate is usually a monosulfonate, but can also contain di-, tri- or higher sulfonates. The paraffin sulfonates can contain, for example, a disulfonate in a mixture with the corresponding monosulfonates, in an amount of up to 30%.

60981 3/1066

In general, these water-soluble inorganic surfactants are salts of alkali cations such as potassium, optionally lithium and especially sodium, albeit also salts of ammonium cations and substituted ammonium cations of lower alkano! amines with 2 to 4 carbon atoms such as triethanolamine, Tripropanolamine and diethanolmonopropanolamine and lower alkylamines containing 1 to 4 carbon atoms such as methylamine, sec-butylamine, dimethylamine, tripropylamine and triisopropylamine can also be used.

The olefin sulfonates are water soluble surfactants that usually contain long chain alkyl sulfonates and long chain hydroxy alkane sulfonates. The latter have the hydroxyl radical on a carbon atom that is not directly bonded to the carbon atom that bears the sulfonic acid radical. Usually the olefin sulfonate detergents contain a mixture of these two compounds, often together with long chain disulfonates or sulfate sulfonates. Such olefin sulfonates are described in numerous patents and by Baumann et al in "Fette-Seifen-Anstrichmittel", Volume 72, No. 4, pages 247-253 (1970). The number of carbon atoms in the olefin sulfonates is usually in a range from 10 to 25, in particular between 14 or 16 to 22, such as, for example. a mixture of essentially C ₁₄ , C ₁₆ and C. o with an average of about 16 carbon atoms.

609813/1066

Although it is generally not necessary, other anionic surfactants besides the paraffin and olefin sulfonates mentioned to use, other anionic surfactants in a total amount up to the total amount of paraffin sulf onate and olefin sulfonate, but preferably less than half of this total including the soaps are used.

Other suitable anionic surfactants are higher alkyl benzene sulfonates, the alkyl radicals of which contain 10 to 20 and preferably 10 to 16 carbon atoms, the alkyl radical preferably a straight-chain alkyl radical with 11 to 13 or up to 14 Carbon atoms and the alkylbenzenesulfonates preferably have a high content of 3-isomers or higher phenyl isomers and a correspondingly low content, usually well below 50%, of 2-phenyl isomers or lower isomers contain. In these compounds, the benzene ring is preferably in a 3-position or higher such as a 4-, 5-, 6- or 7-position substituted by the alkyl radical, while the content of isomers in which the benzene ring in a 1 or 2 position is extremely low.

Other suitable anionic surfactants are water-soluble salts of higher fatty acids such as lauric, myristic, stearic, oleic, Elaidic, isostearic, palmitic, undecylene, tridecylene,

• '609813/1068

Pentadecylenic acid, higher alkanoic acids in the 2-position with lower alkyl radicals are substituted, such as 2-methyltridecanoic acid or 2-methylpentadecanoic acid and 2-methylheptadecanoic acid or other saturated or unsaturated fatty acids having 10 to 20 carbon atoms. Soaps can also be used of dicarboxylic acids such as soaps of dimerized linoleic acid; as well as soaps of other high molecular acids such as rosin acid and tall oil acid such as abietic acid. Other anionic surfactants are sulfates of higher alcohols such as Sodium lauryl sulfate, sodium tallow alcohol sulfate, sulfated oils, sulfates of mono- or diglycerides of higher fatty acids such as stearic acid monoglyceride monosulfate; higher alkyl polyetheneoxyether sulfates such as sulfates of the condensation products of ethylene oxide and higher aliphatic alcohols such as lauryl alcohol, where the molar ratio from ethylene oxide to alcohol in a range from 1: 1 to 5: 1 lies; Alkylglyceryläthersulfonate of higher alkylenes such as lauryl and aromatic Polyäthenoxyäthersulfate such as Sulphates of condensation products of ethylene oxide and nonylphenol, which usually contain 1 to 20 and preferably 2 to 12 oxyethylene radicals per molecule. The ether sulfates can also be one lower alkoxy group of 1 to 4 carbon atoms such as methoxy group on a carbon atom close to the carbon atom contain that carries the sulfate residue, such as monomethyl ether monosulfate of a long-chain vicinal

60981 3/1066

Glycol such as a mixture of vicinal alkanediols with 16 or 17 to 18 or 20 carbon atoms in a straight chain.

Other suitable anionic surfactants are higher alkyl sarcosinates such as sodium lauroyl sarcosinate, and acyl esters such as, for example Oleic acid esters of isethionates and acyl-N-methyltaurides such as potassium-N-methyllauroyl- or -oleyl tauride. Other anionic surfactants are higher alkyl phenol sulfonates such as higher alkyl phenol disulfonates, it being possible for the disulfonate to have a blocked phenolic hydroxyl group, for example by etherification or esterification. The Η atom of the phenolic OH group can therefore be replaced by an alkyl group, for example by an ethyl group or by a Hydroxypolyalkoxyalkylrest be replaced and the resulting alcoholic OH radical can be esterified and that Form sulfate.

Although the organic carboxylates, sulfates and sulfonates mentioned are generally preferred anionic surfactants, the corresponding organic phosphates and phosphonates may also be suitable.

Furthermore, in addition to the anionic surfactants, nonionic or amphoteric detergent substances can also be present

609813/1066

be. If appropriate, cationic surfactants or conditioning agents can also be used, albeit these mostly due to possible side effects with the anionic compounds should be avoided if they are not encapsulated or otherwise isolated from the anionic compounds. The nonionic surfactants are common pasty masses or solids sticky at room temperature with melting points below about 40 ° C, albeit at higher temperatures solid products may be suitable. Typical nonionic surfactants are polyethyleneoxy derivatives, obtained by the condensation of ethylene oxide with compounds containing hydrophobic hydrocarbon chains and have one or more active hydrogen atoms, such as higher alkylphenols, higher fatty alcohols, higher fatty acids, higher fat mercaptans, higher fatty amides and polyols such as fatty alcohols with 8 to 20 and usually 10 to 18 carbon atoms in the alkyl radical, the average are ethoxylated with 3 to 20 and usually 5 to 15 ethylene oxide units. Commercially available nonionic surfactants of this type are "Neodol 45-11", namely a fatty alcohol with 14 to 15 carbon atoms of the 11 ethylene oxide units on average possesses, "Neodol 25-7", namely a fatty alcohol ethoxylated with 7 ethylene oxide units with 12 to 15 carbon atoms in the chain; "Alfonic 1618-65", an alkanol ethoxylated with 10 to 11 ethylene oxide units with 16 to 18

609813/1066

Carbon atoms as well as "Pluronic B-26", one with ethylene oxide and propylene oxide etherified alcohol having 12 to 13 carbon atoms.

The amphoteric surfactants are usually higher fatty carboxylates, Phosphates, sulfates or sulfonates that contain a cationic radical such as an amino radical that can be quaternized, for example with a lower alkyl group, or its chain on the amino radical by condensation with a lower one Alkylene oxide such as ethylene oxide is extended. In some cases the amino group can be part of a heterocyclic Be a ring. Typical commercial water-soluble amphoteric surfactants are "Deriphat 151", namely a sodium N-coconut ß-aminopropionate, and "Miranol C2M", namely the anhydrous form of a heterocyclic diamino-dicarboxylate.

The molecular sieves used according to the invention are preferably water-insoluble crystalline aluminum silicate zeolites Of natural or synthetic origin, the latticework of which is essentially uniform pore sizes in the range from 3 to 10 A and their size is determined by the crystal structure of the zeolite. Of course you can also use zeolitic Molecular sieves with one or more different sized lattice structures or mixtures of different zeolites are used will.

609813/1066

The zeolite molecular sieve can also be an exchange zeolite for monovalent cations, i.e. an aluminum silicate with a monovalent cation such as sodium, potassium, lithium or other alkali metals, ammonium or hydrogen. The sodium or potassium aluminum silicates are preferred.

Preferred zeolite structures are molecular sieves A, X, Y, L, Mordenite, Chabazite and Erionite and other zeolitic molecular sieves such as those in Table 9.6 in "Zeolites Molecular Sieves "by Donald W. Breck, published by John Wiley & Sons (1974) are described.

Zeolitic molecular sieves with an Al ₃ O ₃ : SiO 2 molar ratio of 1: 2 to 1: 4 are preferred. Mixtures of these molecular sieves and equivalent zeolites can also be used. The preferred crystalline structures of zeolites are known from the art of ion exchangers. Synthetic molecular sieves of type A as described on page 133 of Breck (loc. Cit.) Are particularly preferred. The best results are obtained with a 4A molecular sieve in which the cation of the zeolite is sodium and the pore size is about 4 S; these zeolites are described as zeolite A in U.S. Patent 2,882,243.

609813/1066

The zeolitic molecular sieves can either be in their dehydrated, calcined form with a moisture content of 1 to 3% or loaded with water, in which case they are then adsorbed up to 36, for example 4 to 30% Contains water depending on the type of zeolite. Preferably, the dehydrated form of the molecular sieves with a Content of about 2% water used. The production of such crystals is known; for the production of Zeolite A. those formed in a crystallization medium such as a hydrous amorphous sodium aluminum silicate gel hydrated zeolite crystals are dehydrated or calcined, as is customary, for example, in the preparation of catalysts is. The hydrated zeolites, either fully or partially hydrated, can be filtered off the crystals can be obtained from the crystallization medium and drying in air at room temperature without calcining, so that the water content is in the range from 4 to 30, for example 20 to 28.5%. It seems that the drier zeolites improve the flow properties of the detergent more than the more water-containing zeolites, presumably because more open pores are present.

The crystalline molecular sieves should essentially not contain any adsorbed gases such as carbon dioxide, as such Gas-containing zeolites on contact with water to form an over-

609813/1066

moderate foaming. The molecular sieve zeolites should preferably be in finely divided form, namely as crystals with an average particle diameter in one Range from 0.5 to about 12 and preferably 5 to 9 and most preferably 5.9 to 8.3 microns. Zeolite sieves with a particle diameter of 5.9 to 6.4 microns are general Better builders for detergents, as they also prevent the washing powder from caking or clumping and improve the flow properties; however, in other cases, zeolites with a diameter of 8.3 microns are preferred.

The silicas used instead of or in addition to the molecular sieves are the pyrogenic or "smoky" silicas having a particle size of 0.1 to 10 and preferably 0.1 to 2 microns; albeit using the actual Molecular sieves is preferable. These products, also known as colloidal silicas, are sold under the trade names "Cab-O-Sil" e.g. "Cab-O-Sil CH-5" or "Cab-O-Sil M-5 "or" Zeosyl 100. "Although it is much more convenient to use the molecular sieves alone and without pyrogenic or colloidal silica, in many cases it is possible to use up to half the normal content to replace molecular sieves with colloidal silica and in some cases the entire molecular sieve content

609813/1066

exchanged, but not always just as good products are obtained.

In addition to the ingredients mentioned above, it is important to include a water-soluble sodium silicate as a suitable builder salt or washing alkali. These builder salts should have an Na ₂ O: SiO ₂ ratio in the range from 1: 1.6 to 1: 2.8 and preferably 1: 2 to 1: 2 _# 6 and in particular 1: 2.5. Such a silicate with a Na ~O: SiO ratio of 1: 2.5 is sold as a polysilicate under the name "Huber CH-171-12-2". Other washing alkalis can be used together with the sodium silicate and in some cases a relatively small amount of up to 30% of the total alkali silicate content of potassium silicate with a corresponding alkali oxide / Si0 ₂ ratio can be used. Other additional builder salts that can be used are sodium bicarbonate, borax, sodium gluconate, and sodium citrate. In some cases where the use of phosphates, nitrogen-containing builders or carbonates can be tolerated, pentasodium _{tripolyphosphate /} tetrapotassium pyrophosphate, tetrasodium pyrophosphate, trisodium nitrilotriacetate and sodium carbonate can be used, but preferably in a total amount which does not exceed the amount of the silicate present. In general, however, phosphates, nitrogen-containing compounds and carbonates should be avoided. One of the essential

60981 3/1066

Union advantages of the present invention is based on the fact that you have excellent washing properties just without such builders that otherwise only contains products containing phosphate and similar synthetic organic detergent raw materials would be obtained.

The coarse detergents according to the invention can also contain other customary detergent additives in small amounts of, for example Contain 0.05 to 8%. The total amount of such additives should not be 20% and preferably not 10% by weight of the Exceed product. Such additives are inorganic pigments such as ultramarine blue, organic pigments such as, for example Indanthrene blue RS and dyes such as "Color Index Direct Blue 1" and in particular optical brighteners such as coumarin, triazolylstilbene, stilbencyanuric acid, Acylaminostilbene, preferably in an amount of about 0.05 to 1%, for example in an amount of 0.1 to 0.5% can be used.

These auxiliaries also include agents that prevent dirt from building up prevent, such as sodium carboxymethyl cellulose, polyvinyl alcohol, hydroxymethyl ethyl cellulose, polyvinylpyrrolidone, Polyacrylamide, hydroxypropylethyl cellulose and mixtures thereof, sodium carboxymethyl cellulose being preferred,

09813/1066

Further additives are perfumes, fungicides or protective substances such as polyhalosalicylanilides such as tetrachlorosalicylanilide, disinfecting or antibacterial substances such as trichlorocarbanilide, foam depressors such as N, N-dilauryl (or di-coconut alcohol) amines; Enzymes such as subtilisin protease, Bleaching agents such as N-bromo and N-chloroimido compounds such as di- and trichloro- (or -bromo) cyanuric acid and its water-soluble salts and plasticizers such as 1,2-alkanediols having 15 to 18 carbon atoms and agents for Improvement of the flow properties like clays e.g. "Satintone".

Furthermore, fillers such as sodium sulfate and sodium chloride or other alkali sulfates and chlorides can be used; further the products contain moisture as usual.

The proportions of the various components of the invention Rough detergents are used to achieve the desired excellent washing properties and flow properties of the product in the following ranges: 8 to 20 wt. ' water soluble paraffin sulfonate (WAS); 4 to 12% by weight of water soluble Olefin sulfonate (WAS); 12 to -30% by weight of water-soluble sodium silicate and 5 to 20% by weight of water-insoluble molecular sieve and / or colloidal particle size silica. The rest of the mixture consists of water, usual additives, Builders, filler salts and the like. The moisture

60981 3/1 0 β p

content is generally between 4 to 22% and that of the filler salts is 5 to 40%. The total amount of additives should not be more than 20% and preferably not more than 10%, the proportions of the individual additives in one Range from 0.05 to 8%. For example, the dirt deposition preventing agent such as Sodium carboxymethyl cellulose is usually present in an amount of from 0.2 to 3%. The quantities given relate to the anhydrous product, the specified moisture content or water content being both the added water and Water of hydration concerns. For example, zeolitic molecular sieves with a water content of about 21% up to about 26% based on hydrated product.

Preferred quantity ranges for the various components are:

9 to 15% sodium paraffin sulfonate, 5 to 10% sodium olefin sulfonate, 20 to 30% sodium silicate, 8 to 15% molecular sieve, in particular molecular sieve A with a particle size of 5.9 to 8.3 microns and a pore size of about 48, 20 to 35% sodium sulfate, 0.3 to 1% sodium carboxymethyl cellulose and

10 to 20% water. The preferred detergents are essentially phosphate-free, whereby it is generally desirable that the detergents do not contain any phosphates or phosphate-containing materials, no nitrogen-containing compounds such as Nitrilotriacetate and no alkali carbonates such as sodium carbonate

609813/1066

contain. If such substances are present, the detergents should nevertheless contain as few of these substances as possible, i.e. contain less than 10% and preferably less than 3 and in particular less than 1%.

A major advantage of the detergent according to the invention is the simple production of the same, without significant Energy expenditure, as is normally the case with spray drying detergents. The various components of the Detergents according to the invention can be used in powdered form and in some cases as a slurry or solution so that the production can be carried out by mechanical mixing and grinding without a substantial expenditure of energy can. The free-flowing coarse detergent according to the invention can be prepared by mixing the silicate and the molecular sieve powder and / or silicon dioxide powder in a conventional ribbon mixer or Lodige mixer or in a shredding plant, for example a micro-shredding device, whereupon the usually sticky paraffin sulfonate with the premix is mixed until again a powdery product results. Then the other ingredients of the detergent added to give a free flowing powder. These operations can be carried out at temperatures from 0 to 90 C and preferably take place at room temperature, for example between 15 and 30 ° C.

609813/1066

The particle size of the various constituents used is, if not already indicated above, preferably in a range corresponding to a mesh number of 6 to 200 and preferably 12 to 160 mesh (US standard), with many the smaller and more finely divided particles adhere to the larger particles, so that no dust formation occurs. Mixing and grinding times will vary, but generally the product will be between rollers that are spaced apart from 0.03 to 0.3 mm, carried out in a period of 30 seconds to 5 minutes. The mixing time for each Additions are between 10 seconds to 5 minutes and the entire mixing time, with the exception of the crushing, is in one Range from 2 to 30 minutes.

Apart from the above-mentioned order of addition of silicate, molecular sieve and / or silica powder and paraffin sulfonate For example, the order of addition of the other ingredients is not critical, although it is generally desirable is to balance the additions of poorly flowing and better flowing materials, so that a non-clumping mass is obtained in the mixing plant. For this reason, it is also advisable to only use the individual components in portions add to maintain the required fluidity of the mixture.

609813/1066

The final product obtained, namely a free flowing powder, can be packaged immediately after mixing has been completed or after a corresponding cooling time and is ready for use immediately.

Washing laundry with the detergent according to the invention is carried out in the same way as with commercially available heavy-duty detergents. The washing water can have a hardness of 3 to 300 ppm, calculated as calcium carbonate usually considered to have a combination of calcium hardness and lower magnesium hardness. One can use heated or cold washing water, usually at room temperature or slightly above. A water with a hardness of 50 to 200 and preferably 50 to 150 ppm at temperatures of 10 up to 90 ° C and usually 15 to 40 or 50 C results in a washing machine with a capacity of 55 to 75 liters and a detergent amount of 0.05 to 0.5 and preferably 0.1 up to 0.2%, especially 0.15% with a 5 to 60 and preferably 5 to 45 minute agitation excellent results. After washing and rinsing is complete, the laundry is preferably dried in an automatic spin dryer. Comparative tests with commercially available heavy-duty detergents, in particular cold detergents for colored laundry are more suitable, showed a much better whiteness of the washed when using zeolitic molecular sieves Laundry than with commercially available laundry detergents containing phosphate

609813/1066

average. When drying in a drying drum, the result was
after washing no problems with any deposits despite the use of insoluble detergent ingredients. The detergents according to the invention are also used
despite the use of the normally sticky detergent raw materials, free-flowing products, so that good commercial coarse detergents result.

It is surprising that you according to the invention with a very
much lower energy expenditure using simpler
Devices can produce a coarse detergent from commercially available ingredients extremely economically. The manufacturing process also does not lead to air pollution, as any dust losses can be prevented much more easily,
than with a spray tower. The coarse detergents are used in the same way as with the usual spray-dried detergents, but the waste water does not contribute to environmental pollution. These desired effects are based on the combination of paraffin and olefin sulfonate detergent raw materials with silicate and insoluble builders, of which the zeolitic molecular sieves are particularly preferred, since they contribute significantly to the scaffolding effect and, together with the silicate, increase the cleaning power and thus equally good or
result in better coarse detergents.

609813/1066

example 1

A detergent was made from the following ingredients:

Weight%

Paraffin sulfonate C ₁₅ (1) 12.0

higher olefin sulfonate (2) 6.0

Polysilicate (3) 25.0

zeolitic molecular sieve 4A (4) 10.0

Sodium carboxymethyl cellulose 0.5

optical brightener (5) 1.0

Perfume 0.5

Sodium Sulphate, Anhydrous 26.7

Humidity 15.0

other additives (6) 3.3

100.0

(1) The paraffin sulfonate used was a normally sticky sodium paraffin sulfonate in which the n-alkyl radical Contained 14 to 20 carbon atoms and the average Carbon number was 15.

(2) As the olefin sulfonate, a sodium olefin sulfonate was used which was obtained by sulfonating an oC-olefin with 15 to 20 carbon atoms with about a molar proportion of highly diluted sulfur trioxide, subsequent neutralization with excess sodium hydroxide and heating the alkaline mixture above 150 ° C to open the Sulton rings was obtained.

(3) The polysilicate had a Na ₂ O: SiO ₂ ratio of 1: 2.5.

(4) The zeolite molecular sieve 4A was a sodium zeolite with 2% moisture based on the anhydrous product

609813/1066

and an average particle diameter of 8.3 microns.

(5) The optical brightener consisted of 0.93% Tinopal 5BM concentrated and 0.07% Tinopal RBS.

(6) The other ingredients were unreacted oils, sodium chloride and by-products from sulfonation.

The polysilicate and the zeolite were mixed with one another in a mixing vessel in the weighed amount for 2 minutes; afterward the paraffin sulfonate was mixed in and on a three-roll mill with a roll spacing of 0.2 mm for 7 minutes Grind until the paraffin sulfonate has been processed into a powder with the other ingredients. Then the Olefin sulfonate was added and the mixture was circulated for 2 minutes, whereupon a mixture of carboxymethyl cellulose and optical Brighteners were added and tumbled for an additional 2 minutes. Sodium sulfate was then mixed in and 2 more Mixed minutes, whereupon perfume is sprayed onto the mass circulated in the mixer and more 5 minutes was mixed. A portion of the water was added with the paraffin sulfonate and olefin sulfonate while a further part was present in the zeolite.- Further required amounts of water can at the end of the process, preferably before Addition of the fragrances are added.

The product obtained is a free flowing powder which passes completely through a 12-mesh sieve,

609813/10 6 B

while only a small fraction passes through a sieve with one mesh number of 140 and virtually no material passes through a 200 mesh screen; apparently they stick extremely finely divided molecular sieve particles on the other particles or agglomerates of the detergent mixture so firmly indicates that no dusty product is obtained.

A commercially available cold detergent containing the sodium salt of linear tridecylbenzenesulfonic acid was used for comparison tests in an amount of 9%, ethoxylated alcohol (Neodol 45-11) in an amount of 4% and 33.6% Pentasodium tripolyphosphate, 7% sodium silicate (Na ~ O: SiO „= 1: 2.4), 34.8% sodium sulfate, 0.5% sodium carboxymethyl cellulose and about 1% optical brightener and about 10% Contained water.

The comparison washes were washed for 30 minutes at 32 ° C. with a detergent concentration of 0.15%; the wash water had a hardness of 110 ppm, calculated as calcium carbonate, but with a calcium / magnesium ratio of 3: 2. In these comparison washes it was found that cotton the detergents according to the invention are extremely clearly a commercial product in the removal of mixed dirt were superior. They are essentially comparable to washing nylon from clay treated cotton

609813/106 6

or non-iron mixed fabrics treated with clay and other test textiles (EMPA). Due to complex comparisons of Brightness values that were obtained when washing numerous textiles that were in turn provided with various test soils, it was possible to conclude that the detergents according to the invention are considerably better under the stated washing conditions up to comparable to common pentasodium tripolyphosphate detergents was.

In a modification of the above composition, a paraffin sulfonate having an average of 17 carbon atoms and an olefin sulfonate having 14 to 22 carbon atoms were used and used an average of 18 carbon atoms. That so Modified detergent had essentially the same properties as the product according to the example. Also a replacement of the polysilicate by one with a Na ~ O: SiO ~ ratio of 1: 2.35 gave a product that was superior to a commercially available cold detergent. Also a replacement for the molecular sieve 4A due to zeolites X or Y led to similar builder effects and equally good products with the same particle size as when using molecular sieves with a particle size of 6.2 microns. When replacing half of the sodium sulfate pentasodium tripolyphosphate gives an improved product. With such a product it is sometimes useful to 1/4 of the proportion of paraffin sulfonate and higher in each case Replace olefin sulfonate with sodium tridecylbenzenesulfonate.

609813/1086

If the moisture content is increased by 6 to 20%, the washing properties of the product remain unchanged, however, the higher the moisture content, the flow property is somewhat reduced.

Other changes in the proportions and the constituents within the scope of the specified invention also lead to satisfactory results Heavy duty detergents. Although it is undesirable, phosphorus-containing or nitrogen-containing builder salts and Furthermore, to use alkali carbonates, these can of course be used because of their properties.

Example 2

A coarse detergent with the following composition was prepared:

Weight%

Paraffin sulfonate C ₁₅ (1) 18.2

higher olefin sulfonate (2) 9.1

Polysilicate (3) '18.2

finely divided silica (7) 9.1

Sodium carboxymethyl cellulose 1, 5

optical brightener (5) 0.9

Perfume 0.5

Sodium Sulphate, Anhydrous 34.3

Water 7.0

other substances (6) 1, 2

609813/1066 100.0

(7) As silicon dioxide it was named under the name "Zeosyl 100" product sold by Huber Chemical Corporation was used.

In the detergent of this composition, finely divided silicon dioxide was used instead of the zeolitic molecular sieve with a grain diameter of less than 100 microns and increased the proportion of anionic detergent raw material to compensate. The product made by the procedure of Example 1 was essentially as effective as the commercial one Comparative product. When the finely divided silicon dioxide is replaced by a zeolitic molecular sieve 4A according to FIG Example 1 was an improvement in the cleaning effect due to the better builder properties of the zeolitic Molecular sieve found. On the other hand, the silica improved the flowability of the product almost up to the extent obtained with a molecular sieve.

When using this detergent with hot water at temperatures of 60 to 70 ^° C., a good cleaning effect results, but this is also the case with a composition according to Example 1.

When replacing half the amounts of paraffin sulfonate and olefin sulfonate by sodium dodecylbenzenesulfonate and "Neodol 45-11",

60981 3/1066

that as a melt to the rest of the product in a circulation system is added shortly before the perfume is added, an effective heavy duty detergent is also obtained. The same is that Case when half of the nonionic WAS in such a modified composition is replaced by an amphoteric surfactant e.g. "Miranol C2M" is replaced.

If there are other changes in the composition, for example if sodium carboxymethyl cellulose is replaced by polyvinyl alcohol, Hydroxyethylmethylcellulose and polyvinylpyrrolidone are also good detergents with, in some cases, not quite so good dirt build-up prevention. Something similar applies also when using other optical brighteners or when replacing half of the sodium sulfate with sodium chloride.

Example 3

Detergents according to Examples 1 and 2 were used in equal amounts in a ratio of 2: 1 and in a ratio of 1: 2 mixed. Detergents which were satisfactory in every respect and which were in every respect the comparative detergent were obtained were comparable or superior in terms of cleaning power.

609813/1066

Example 4

Compositions according to Example 1 and 2 were from a

aqueous slurry with 50% solids, which was ^{premixed at 80 0} C, at 200 C in a countercurrent spray tower

sprayed at a pressure of 100 kg / cm. The small beads obtained having a particle size corresponding to a range between 10 and 100 meshes had a moisture content of 12%, the proportion of the other components correspondingly was increased. This product is a good detergent for laundry, but its production uses more energy and because of the Risk of pollution with more complicated facilities can be produced.

60 9 813/1066

Claims (6)

" ³⁰ " 254O51Ö Claims 1, detergent or coarse detergent for textiles, characterized in that it contains 8 to 20% by weight of a water-soluble Paraffin sulfonate, 4 to 12% by weight of a water-soluble olefin sulfonate, 12 to 30% by weight of a water-soluble Sodium silicate with a Na “0: SiO ratio in one Range from 1: 1.6 to 1: 2.8 and about 5 to 20% by weight of a water-insoluble molecular sieve and / or a silicon dioxide with a colloidal particle size, while the rest of the mixture contains water, common detergent additives, Can be builders or filler salts. 2. Detergent according to claim 1, characterized in that the water-soluble paraffin sulfonate is an AlkaÜparaf insulfonat with 14 to 22 carbon atoms, the olefin sulfonate is an alkali metal sulfonate with 14 to 22 carbon atoms, the sodium silicate is a Na ₂ O: SiO ₂ ratio from 1: 2.0 to 1: 2.6 and the molecular sieve is a sieve of type A, X or Y and that the detergent has 4 to 22% moisture, 5 to 40% sodium sulfate and / or sodium chloride as filler salt and 0, Contains 2 to 3% water-soluble agents to prevent the build-up of dirt. 6098 13/106 6 3. Detergent according to claim 2, characterized in that there are 9 to 15% sodium paraffin sulfonate with 16 to 22 carbon atoms, 5 to 10% sodium olefin sulfonate of an olefin with 16 to 22 carbon atoms, 20 to 30% sodium silicate with a Na ₂ O: SiO ₂ ratio of 1: 2.5 and 8 to 15 % of a molecular sieve A having a particle size in the range 5.9 to 8.3 microns and a nominal pore size of about 4R, as well as 20 to 35% sodium sulfate, 0.3 to 1% sodium carboxymethyl cellulose and 10 to 20% water. 4. A method for washing soiled cotton, characterized in that the laundry is washed in an automatic washing machine for 5 to 45 minutes in a washing water which contains 0.1 to 0.2 % of a detergent containing 8 to 20% water-soluble paraffin sulfonate, 4 to 12% of a water-soluble olefin sulfonate, 12 to 30% of a water-soluble sodium silicate with a Na ~ O: SiO ~ ratio in the range from 1: 1.6 to 1: 2.8 and about 5 to 20% of a water-insoluble molecular sieve and / or silica in colloidal particle size, while the remainder are conventional detergent additives, builders or filler salts or water. 609813/1066 5. The method according to claim 4, characterized / that 'one washes with a water hardness of 50 to 200 ppm, calculated as calcium carbonate with a detergent concentration of about 0.15% at temperatures of 15 to 40 C with a substantially phosphate-free detergent, which 12% sodium paraffin sulfonate containing 16 to 22 carbon atoms, 6% sodium olefin sulfonate containing 16 to 22 carbon atoms, 25% sodium silicate with a Na _{2 OrSiO 3} ratio of 1: 2.5 and about 10% of a type A molecular sieve with a nominal pore size of about 4 2 and a particle size of about 8.3 microns, contains about 27% sodium sulfate, 15% moisture, and about 0.5% sodium carboxymethyl cellulose. 6. Process for the production of a free-flowing coarse detergent with a content of 8 to 20% of a water-soluble paraffin sulfonate, 4 to 12% of a water-soluble olefin sulfonate, 12 to 30% of a water-soluble sodium silicate with an Na ₂ O: SiO2 ratio in the range of 1: 1 , 6 to 1: 2.8 and about 5 to 20% of a water-insoluble molecular sieve and / or a silicon dioxide with colloidal particle size, while the remainder is moisture, customary washing aids, builders and / or filler salts, characterized in that the silicate and the Molecular sieve and / or the silicon dioxide powder mixed, 609813/1066 then the paraffin sulfonate is added to the premix during grinding until a powdery mixture is obtained whereupon the other ingredients of the detergent are added. 609813/1066