JP2001158900A - Defoaming granulate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide defoaming granulates for solid detergents, detergents for dishes and detergent compositions containing a carrier material and a silicone. SOLUTION: The defoaming granulates are obtained by applying a silicone in an aqueous emulsion form to intermediate product of a carrier material added and drying and granulating the silicone by a fluidized bed. At least 85 wt.% average particle diameter of the granulates is <1.5 mm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to solid laundry detergents, dishwashing detergents and cleaning compositions, in particular as obtained by drying and granulating at the same time.
Novel silicone-containing antifoam granules for solid laundry detergents, dishwashing detergents and cleaning compositions.

(Prior Art) Generally, household and commercial laundry detergents, dishwashing detergents, detergents (cleaners) and the like include organic surfactants, builders, organic additives, inorganic additives and the like. I have. Surfactants commonly used in laundry, when used, form foam which adversely affects the cleaning effect. Therefore, in actual applications, it is necessary to suppress foaming. Silicones have proven to be particularly suitable antifoaming agents and are commonly used as coatings on carrier materials. If desired, other foam control substances, such as those used in solid laundry detergents, dishwashing detergents and cleaning compositions, are also coated on the carrier material.

[0003] For example, DE 3128631 A1 discloses a process for the production of foam control detergents comprising a microencapsulated silicone antifoam. According to this document, silicone is dispersed in an aqueous dispersion of a film-forming polymer, and the resulting dispersion is spray-dried through a pipe separate from an aqueous solution or aqueous dispersion of another detergent component. Send to the tower. The two fluids are then mixed near the spray nozzle. Suitable film-forming polymers include cellulose ethers, starch ethers, water-soluble synthetic polymers, and the like. Microcapsules are formed automatically at the spray nozzle. The application of the above method is limited to the method of producing a spray-dried detergent, and seems to be inapplicable to detergents produced by other methods such as granulation. The silicone-containing antifoaming agent disclosed in EP 0496510 A1 applies a mixture of silicone and a fatty alcohol, fatty acid, glycerol monoester or the like having a specific melting point to a starch carrier material. To produce such antifoam granules, silicone and other organic components are mixed with starch in liquid form and granulated by a fluid bed process. The problem with this method is that during granulation, the silicone and organic materials are sprayed onto the carrier material. That is, silicone is
Due to its high viscosity and a sticky oily consistency, its pumping is difficult and, at the spray nozzle, it shows spinnability and forms sticky deposits.
As a result, the precise spraying required is substantially more difficult.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid laundry detergent and a dishwashing detergent which exhibit particularly good fluidity and do not generate dust. And novel antifoam granules for cleaning compositions. The problem to be solved by the present invention is also to provide a method for producing antifoam granules designed so that the silicone can be easily pumped and sprayed precisely.

(Means for Solving the Problems) The present invention provides:
In foam control granules for solid laundry detergents, dishwashing detergents and cleaning compositions comprising a carrier material and silicone,
The antifoam granules are obtained by applying an aqueous emulsion form of the silicone to the added intermediate product of the carrier material, drying it by a fluid bed and simultaneously granulating, and at least 85% of the particles. weight%
The average particle size (average diameter) of (preferably at least 90% by weight, more preferably at least 95% by weight) is less than 1.5 mm (preferably less than 1.3 mm, more preferably 0.1-1.5 mm). The present invention provides an antifoam granule.

[0006] Surprisingly, it has been found that the new regulated effervescent granules of the present invention completely satisfy the desired requirements.

[0007] The present invention also provides a process for producing antifoam granules for solid laundry detergents, dishwashing detergents and detergent compositions (including carrier materials and silicones), comprising the steps of: Applying to the added intermediate product of the carrier material, drying and granulating while drying by a fluidized bed, and at least 85% by weight (preferably at least 90% by weight, more preferably at least 95% by weight of the particles) %) Is less than 1.5 mm (preferably
(Less than 1.3 mm, more preferably 0.1-1.5 mm). Silicones Suitable silicones in the present invention are representative organopolysiloxanes containing silica particulates, which may be silane-treated. The corresponding organopolysiloxanes are described, for example, in the above-mentioned European patent application EP 0 4
96510 A1. Polydiorganosiloxanes known from the prior art are particularly suitable. Preferred polydiorganosiloxanes have approximately linear chains and a degree of oligomerization of 40-1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert-butyl and phenyl. Polydiorganosiloxanes generally contain fine silica particles, which may be silanized. Silica-containing dimethylpolysiloxane is particularly suitable for the purposes of the present invention. Polydiorganosiloxane at 25 ° C
Those having a Brookfield viscosity (spindle 1, 10 rpm) of from 5000 mPas to 30,000 mPas, in particular from 15,000 mPas to 25,000 mPas, are advantageous. An important feature of the present invention is that the silicone is sprayed as an aqueous emulsion. Generally, the silicone is added to the water with stirring. If desired, so-called thickeners known from the prior art may be added to increase the viscosity of the aqueous silicone emulsion. Thickeners can be inorganic and / or organic substances, and particularly suitable thickeners are nonionic cellulose ethers such as methylcellulose, ethylcellulose, mixed ethers (methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutylcellulose). And the like, and anionic carboxycellulose types such as sodium carboxymethylcellulose (abbreviation: CMC). Particularly suitable thickeners are mixtures of CMC and non-ionic cellulose ethers in a weight ratio of 80:20 to 40:60, especially 75:25 to 60:40. In general, and especially when the above-mentioned thickener mixtures are added, it is possible to use concentrations of approximately 0.5 to 10% by weight, in particular 2.0 to 6% by weight, as thickener mixture, based on the silicone aqueous emulsion. desirable. The content of silicone of the type described above in the aqueous emulsion can be from 5 to 50 as thickener mixture, based on the silicone aqueous emulsion.
Advantageously, it is in the range from 20% to 40% by weight. In another advantageous embodiment, the aqueous silicone solution comprises starch obtained from natural sources, such as rice, potato, corn, wheat, etc., as a thickener. The starch is advantageously present in an amount of from 0.1 to 50% by weight, based on the silicone emulsion, and in particular in the form of a mixture of the abovementioned amounts of sodium carboxymethylcellulose with the abovementioned thickener mixture of nonionic cellulose ethers. It is. Aqueous silicone emulsions are suitably prepared by pre-swelling any thickeners present before adding the silicone. The silicone is preferably mixed using an effective stirrer and mixer.

Carrier materials Suitable carrier materials according to the invention are any known inorganic and / or organic carrier materials. Examples of representative inorganic support materials are alkali metal carbonates, aluminosilicates, water-soluble layered silicates, alkali metal silicates, alkali metal sulfates (eg, sodium sulfate) and alkali metal phosphates. Alkali metal silicate molar ratio of alkali metal oxide to SiO ₂ 1: 1.5~1: is suitably a compound of 3.5. The use of these silicates leads to particularly good particle properties, in particular to high abrasion resistance, while at the same time providing a high rate of dissolution in water. Zeolite (eg, NaA-type zeolite and N-type zeolite)
aX type zeolite). Compounds described as water-soluble phyllosilicates include, for example, amorphous or crystalline waterglass. Suitable organic carrier materials are, for example, film-forming polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylates, polymethacrylates,
Polycarboxylates, cellulose derivatives and starch. Suitable cellulose ethers are, in particular, alkali metal carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose and so-called mixed cellulose ethers, such as, for example, methylhydroxyethylcellulose, methylhydroxypropylcellulose and the like, and mixtures thereof. A particularly preferred mixture is a mixture of sodium carboxymethylcellulose and methylcellulose, the carboxymethylcellulose usually being added per unit of anhydrous glucose.
Has a degree of substitution of 0.5-0.8 carboxymethyl groups,
On the other hand, methylcellulose is equivalent to 1 unit of anhydrous glucose.
It has a degree of substitution of 1.2 to 2 methyl groups. This mixture preferably comprises a weight ratio of alkali metal carboxymethylcellulose and nonionic cellulose ether of 80:20 to 40:60, in particular 75:25 to 50:50. The corresponding cellulose ether mixtures can be used in solid form or as aqueous solutions which can be pre-swelled in the customary manner. According to the present invention, native starch consisting of amylose and amylopectin is a particularly suitable carrier. Natural starch is starch that can be obtained as an extract from natural sources such as rice, potato, corn, wheat and the like. Natural starch is a standard commercial product and is readily available. Suitable carrier materials are, in particular, alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble layered silicates, alkali metal silicates, polycarboxylates, carboxymethylcellulose, polyacrylates / polymethacrylates. And the individual compounds described above, selected from the group of starch,
Or some of these compounds. Alkali metal carbonates (especially sodium carbonate), alkali metal silicates (especially sodium silicate), alkali metal sulfates (especially sodium sulfate), zeolites, polycarboxylates (especially polyacrylates, polymethacrylates), cellulose ethers and natural Mixtures of starches are particularly preferred. The carrier material can have the following composition: cellulose ether 0-2% by weight native starch 0-75% by weight alkali metal silicate 0-30% by weight alkali metal sulfate 0-75% by weight alkali metal carbonate 0- 95% by weight Zeolite 0-95% by weight Polycarboxylate 0-5% by weight, but the total must be 100% by weight.

In addition to the wax-like foam control agent a silicone, water-insoluble foam control agent compound waxy can also be used in accordance with the present invention. A “wax-like” compound is one that is above 25 ° C. (room temperature) at atmospheric pressure, preferably
A compound having a melting point above 50 ° C., more preferably above 70 ° C., is taken to be a compound. The waxy antifoam optionally present according to the present invention is substantially insoluble in water. That is, their solubility in 100 g of water at 20 ° C. is 0.1
% By weight. In principle, any wax-like foam control agent known from the prior art can additionally be present. Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic esters of monohydric or polyhydric alcohols and paraffin waxes, or mixtures thereof. Bisamides obtained from saturated fatty acids containing 12 to 22, preferably 14 to 18 carbon atoms and alkylenediamines containing 2 to 7 carbon atoms are preferred. Suitable fatty acids are lauric, myristic, stearic, arachidic and behenic acids, and mixtures thereof which can be obtained from natural fats or oils, such as tallow or hydrogenated coconut oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluylenediamine. Preferred diamines are ethylene diamine and hexamethylene diamine. Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine,
Mixtures thereof and their corresponding derivatives of hexamethylenediamine. Suitable carboxylic esters are derived from carboxylic acids containing 12 to 28 carbon atoms. The esters are, in particular, behenic acid, stearic acid,
Esters of oleic, palmitic, myristic and / or lauric acids. The alcohol portion of the carboxylic acid ester includes monohydric or polyhydric alcohols containing 1-28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coco alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol, and ethylene glycol, glycerol, methanol, ethanol, isopropanol, vinyl alcohol, sucrose, erythritol, pentaerythritol, Sorbitan and / or sorbitol. Suitable esters are esters of methanol, ethylene glycol, glycerol and sorbitan, the acid part of which is chosen in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyhydric alcohols are
For example, xylitol monopalmitate, pentaerythritol monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, dioleine Acid sorbitan, and mixed tallow alkyl sorbitan monoesters and diesters. Suitable glycerol esters are monoesters, diesters or triesters of glycerol with the carboxylic acids mentioned above, with monoesters and diesters being preferred. Glycerol monostearate, glycerol monooleate,
Glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples. Examples of suitable natural esters are beeswax and carnauba wax. Carnauba wax is a mixture of carnauba acid alkyl esters, often containing small amounts of free carnaubaic acid, other long-chain acids, and high molecular weight alcohols and hydrocarbons. Carboxylic acids suitable as further antifoam compounds are obtained in particular from behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid and from natural fats such as tallow or hydrogenated palm oil or, if desired, from hydrogenated oils. Be a mixture of them. 12 ~
Saturated fatty acids containing 22, especially 14 to 18 carbon atoms are preferred. Fatty alcohols suitable as another antifoam compound are the hydrogenated products of the fatty acids mentioned above. According to the invention, paraffin waxes which are suitable as further antifoam compounds are generally complex mixtures which do not have a well-defined melting point. For characterization, usually the melting range is determined by differential thermal analysis (DTA) as described in The Analyst 87 (1962) 420 and / or its freezing point is determined. The freezing point is taken to mean the temperature at which the paraffin changes from a liquid state to a solid state by slow cooling. Paraffins that are completely liquid at room temperature, that is, paraffins with a freezing point below 25 ° C., are not suitable for use according to the invention. For example EP 0
2699-49% by weight of microcrystalline paraffin wax with a freezing point of 62-90 ° C., known from 309931 A1, 42 ° C.
A paraffin wax mixture of 20% to 49% by weight solid paraffin having a freezing point of ~ 56 ° C and liquid paraffin having a freezing point of 35 ° C to 40 ° C can be used. 30 ° C ~
Paraffins or paraffin mixtures which coagulate at a temperature of 90 ° C. are preferably used. In this context, it should be noted that a paraffin wax mixture that appears solid at room temperature may also contain varying amounts of liquid paraffin. In a paraffin wax suitable for use in accordance with the invention, the components of this liquid are as low as possible and preferably completely absent. For example, in a particularly preferred paraffin wax mixture, the component liquid at 30 ° C. is less than 10% by weight, in particular 2% to 5% by weight,
Less than 30% by weight of liquid components at 40 ° C., preferably 5% to 2%
5% by weight, more preferably 5% to 15% by weight,
30% to 60% by weight of liquid components, preferably 40% by weight
80% by weight of liquid components at 80 ° C
% At 90 ° C. and 100% by weight of liquid components at 90 ° C.
In a particularly preferred paraffin wax mixture, the temperature at which 100% by weight of the paraffin wax liquid component is reached is below 85 ° C., in particular between 75 ° C. and 82 ° C. Paraffin waxes of the type described above are particularly suitable for the purposes of the present invention.

According to the preparation present invention, first, the intermediate product of support material, and wax-like foam control agent present in the desired is prepared. If the intermediate product additionally comprises a wax-like antifoaming agent, the weight percentage of carrier material is preferably from 20 to 100, based on the intermediate product.
It is preferably 98% by weight, more preferably 35-95% by weight, while the weight percentage of wax-like foam control agent is preferably 2-80% by weight, more preferably 5-65% by weight. The carrier material can be produced in a conventional manner by spray-drying the aqueous slurry. If additional waxy foams are used, they may be applied, for example, by spraying the molten waxy foam to the spray dried granular carrier material, for example by stepwise addition, more preferably in the form of a spray. Can be applied by The carrier material is preferably kept running by mixing the components or by fluidization in order to ensure a uniform impregnation of the carrier material.
The spray mixer used can be operated continuously or discontinuously.

In another preferred embodiment of the invention, the intermediate product, which additionally comprises a wax-like antifoam, comprises dissolving or suspending the carrier material in water and adding the wax-like foam to the resulting solution or suspension. It is manufactured by spray drying the obtained slurry after dispersing the antifoaming agent. A water soluble non-surfactant dispersion stabilizer in the form of a polymer that swells in water may be added to the dispersion. Suitable polymers for this purpose are the above-mentioned cellulose ethers, homopolymers of unsaturated carboxylic acids such as acrylic acid or maleic acid or copolymers of such acids with copolymerizable vinyl compounds such as vinyl ether, acrylamide, ethylene. . The amount of these dispersion stabilizers added to the aqueous slurry is preferably 5% by weight or less, particularly 1% by weight to 3% by weight, based on the intermediate product formed.
It is. Depending on the nature or solubility of the carrier material, the water content of the slurry can be between 30% and 60% by weight. Spray-drying of this dispersion can be carried out in a so-called spray-drying tower in a known manner with hot drying gases flowing cocurrently or countercurrently. Drying with a drying gas flowing co-current to the material to be spray dried is preferred. This is because this method can minimize the loss of activity due to the potential hot air volatility of certain components of paraffins, especially when paraffin-containing intermediate products are used.

According to the invention, the spraying of the aqueous silicone emulsion with drying and granulation onto the solid intermediate product is carried out by means of the so-called SKET process in a fluidized bed, in particular in a continuously operating fluidized bed. It is preferable to carry out. In this method, a silicone aqueous emulsion is introduced into a fluidized bed through one or more nozzles. In the process of the invention, the intermediate product of the carrier material and the waxy foam control agent is added simultaneously with the aqueous silicone emulsion, but separately, preferably by an automatically controlled solids metering system. The product stream of the silicone aqueous emulsion and the added intermediate product is based on the foam control granules, as silicone,
It is preferably controlled so as to obtain foam control granules containing 2.0 to 25% by weight, particularly 5.0 to 20% by weight of silicone.
The remaining part of the antifoam granules (100% by weight in total) is the intermediate product already described. In a fluidized bed, the aqueous silicone emulsion impinges on the added intermediate product and the water evaporates, forming a somewhat dry dry core. The core thus formed is coated with the introduced more aqueous silicone emulsion or the added intermediate product, granulated and again dried simultaneously. This simultaneous drying and granulation takes place in a fluidized bed above a circular diffuser plate with through openings for drying air, and the product to be dried is such that cumulative granulation occurs. During this drying stage, it remains stationary above the diffuser plate. Further details of the so-called SKET method can be found in EP 0603207 B1. One particular advantage of this method is that the foam control granules formed are screened or classified by the incoming drying air with regard to their particle size and thus with regard to their weight, to reach the required size or weight. Granules fall from the fluidized bed to the base plate and then to a discharge lock.

Suitable fluidized beds have a diameter of 0.4 to 5 m, for example
It has a circular base plate (diffuser plate) of 1.2m or 2.5m. This base plate is a perforated plate, Conidur (trade name)
It can be a plate (a product of Hein & Lehmann, Germany) or a perforated plate whose through holes (through openings) are covered with gauze with a mesh width of less than 600 μm. The gauze can be located within or above the through opening. Preferably, however, the gauze is located directly below the through opening in the diffuser plate. This is preferably done by sintering a metal gauze with a suitable mesh width. The metal gauze is preferably made of the same material as the diffuser plate, particularly stainless steel. The mesh width of the above-described gauze is preferably 200 to 400 μm.

According to the present invention, the method comprises:
It is preferred to work with a fluidizing air flow rate of seconds, especially 1.5 to 5.5 m / s. The granules are preferably discharged through a screening stage. Sorting is performed by a countercurrent flow of drying air (sorting air) controlled such that only particles above a certain particle size are removed from the fluidized bed and smaller particles remain there. Is preferred. In a preferred embodiment, the incoming air consists of heated or unheated sorting air and heated bottom air. Suitably the bottom air temperature is between 80 and 400 ° C. The fluidizing air is cooled by heat loss and heat of evaporation, preferably its temperature, measured about 5 cm above the bottom plate, is in the range 60-120 ° C, preferably in the range 65-90 ° C, more preferably 70-90 ° C. In the range of ~ 85 ° C. The air outlet temperature is preferably between 60 and 120C, in particular below 80C.

[0015] The residence time during which the product to be dried is stationary on the diffuser plate is preferably between 5 and 60 minutes. In the present invention, the content of free water is based on the final granules,
As long as it is less than 10% by weight, preferably 0.1-2% by weight, the antifoam granules are considered dry. In a preferred embodiment in which the production is carried out in a fluidized bed, the starting material serving as the initial carrier for the sprayed silicone aqueous emulsion must be present from the beginning of this step. This starting material can consist of the added intermediate product or, in one particular embodiment, the antifoam granules themselves obtained in the previous production cycle.
Preference is given to using antifoam granules having a particle size of more than 0.2 mm and less than 0.9 mm as starting materials, and it is preferable to feed them via a roller mill. Next, the antifoaming agent granules obtained from the fluidized bed are cooled in a separate fluidized bed and, using a sieve, have a particle size of 0.9 mm to 5 mm as an acceptable product.
, A granule having a particle size of greater than 5 mm as a sieve, and a granule having a particle size of less than 0.9 mm as a sieve. The granules in the sub-sieve fraction are returned to the fluidized bed. The sieve fraction is preferably of a size
It is ground to particles of less than 0.9 mm and likewise returned to the fluidized bed.

The suds control agent granules INDUSTRIAL APPLICABILITY The present invention is a free-flowing product in spherical does not release dust. They have a good foam control effect and can be used for both spray-dried and granulated surfactant compositions. Accordingly, the present invention provides solid laundry detergents, dishwashing detergents and their use for producing detergent compositions. The antifoam granules may be present in an amount of 0.2-7.0% by weight, preferably 0.5-4.0% by weight, based on the composition. Mixing of the antifoam granules is easy.

Laundry Detergent, Dishwashing Detergent and Detergent Composition The main components of the laundry detergent, dishwashing detergent and detergent obtained by using the antifoam granules of the present invention are anionic surfactants, nonionic detergents and nonionic detergents. Amphoteric surfactants, cationic surfactants, amphoteric and / or zwitterionic surfactants, but preferably anionic surfactants and combinations of anionic and nonionic surfactants. . Representative examples of anionic surfactants are soap, alkylbenzene sulfonate, alkane sulfonate, olefin sulfonate, alkyl ether sulfonate, glycerol ether sulfonate, α-methyl ester sulfonate, sulfo fatty acid, alkyl Sulfate, fatty alcohol ether sulfate, glycerol ether sulfate, hydroxy mixed ether sulfate, monoglyceride (ether) sulfate, fatty acid amide (ether) sulfate, monoalkyl sulfosuccinate, dialkyl sulfosuccinate, mono and Dialkyl sulfosuccinamate, sulfotriglyceride, amide soap, ether carboxylic acid and its salt, fatty acid isethionate, fatty acid sarcosinate, fatty acid tauride, N-acyl amino acid (for example, acyl lactylate Acyl tartrates, acyl glutamates, such as acyl aspartates), alkyl oligoglucosides sulfates, protein fatty acid condensates (particularly wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactant contains a polyglycol ether chain, the polyglycol ether chain can have a conventional homolog distribution. However, they preferably have a narrow homolog distribution. Alkyl benzene sulphonates, alkyl sulphates, soaps, alkane sulphonates, olefin sulphonates, methyl ester sulphonates and mixtures thereof are preferably used. Suitable alkylbenzene sulfonates correspond to the following formula (I):

Embedded image Wherein R is a branched, but preferably straight-chain, alkyl group containing 10 to 18 carbon atoms, Ph is a phenyl group, X is an alkali metal and / or alkaline earth metal, Ammonium, alkyl ammonium, alkanol ammonium, or glucamonium (glucammoniu
m). Of these alkali benzene sulfonates, the sodium salt forms of dodecylbenzene sulfonate, tetradecylbenzene sulfonate, hexadecylbenzene sulfonate and their industrial mixtures are:
Particularly suitable. Alkyl and / or alkenyl sulphates, often also referred to as fatty alcohol sulphates, are understood to be the sulphation reaction products of primary and / or secondary alcohols and preferably correspond to the following formula (II):

Embedded image Wherein R ² is a linear or branched aliphatic alkyl and / or alkenyl group containing 6 to 22, preferably 12 to 18 carbon atoms, and Y is an alkali metal and / or alkaline earth Metal, ammonium, alkyl ammonium, alkanol ammonium, or glucammonium. Representative examples of alkyl sulfates that can be used in accordance with the present invention include caproic alcohol,
Caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol (palmitol)
eyl alcohol), stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol (elaidyl alcohol), petroselinyl alcohol (petroselinyl alcohol), aralkyl alcohol (arac)
hyl alcohol, gadoleyl alcohol
hol), behenyl alcohol and erucyl alcohol, and the sulfation reaction products of industrial mixtures thereof obtained by high-pressure hydrogenation of aldehydes obtained from the oxo synthesis of Roelen or industrial methyl ester fractions. It may be advantageous to use these sulphation products in the form of alkali metal salts, especially sodium salts. Alkyl sulfates of the sodium salt type based on _{C16 / 18} tallow fatty alcohol or vegetable fatty alcohols with an equivalent C chain distribution are particularly suitable. In the case of the branched primary type, the alcohols are, for example, oxo alcohols that can be obtained by reacting carbon monoxide and hydrogen with an α-olefin by the Shop method. The corresponding alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25
(Registered trademark) and 45 (registered trademark). Another option is Uniche, where carbon monoxide and hydrogen are added to olefins.
Oxo alcohols obtained by the standard oxo method of ma or Condea. These alcohol mixtures are mixtures of highly branched alcohols,
(Registered trademark). Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®. Finally, soap is understood to be a fatty acid salt corresponding to the following formula (III):

Embedded image Wherein R ³ CO is a linear or branched saturated or unsaturated acyl group containing 6 to 22, preferably 12 to 18 carbon atoms, X is an alkali and / or alkaline earth metal, Ammonium, alkyl ammonium or alkanol ammonium. Representative examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoteric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, Sodium, potassium, magnesium, ammonium and triethanol ammonium salts of linoleic, linolenic, eleostearic, arachiic, gadolinic, behenic and erucic acids and their technical mixtures. Coconut fatty acids or palm kernel oil fatty acids in the form of sodium or potassium salts are preferably used.

Representative examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals. , Alkyl oligoglycosides, alkenyl oligoglycosides, fatty acids -N
-Alkyl glucamides, protein hydrolysates (especially wheat-based plant products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactant comprises a polyglycol ether chain, the polyglycol ether chain may have a conventional homolog distribution. However, they preferably have a narrow homolog distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglycosides are preferably used. Suitable fatty alcohol polyglycol ethers correspond to the following formula (IV):

Embedded image Wherein R ⁴ is a linear or branched alkyl and / or alkenyl group containing 6 to 22, preferably 12 to 18 carbon atoms, R ⁵ is hydrogen or methyl, and n is 1 It is a number of ~ 20. Representative examples are caprol alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroserinyl alcohol, linolyl alcohol, linolenyl alcohol, eleostearyl alcohol, aralkyl alcohol, gadreyl alcohol,
It is a product obtained by adding on average from 1 to 20 mol, preferably from 5 to 10 mol, of ethylene and / or propylene oxide to behenyl alcohol, erucyl alcohol and brassidyl alcohol and their industrial mixtures. Products obtained by adding 3, 5 or 7 moles of ethylene oxide to industrial coconut fatty alcohol are particularly suitable.
Suitable alkoxylated fatty acid lower alkyl esters are surfactants corresponding to formula (V):

Embedded image Wherein R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl group containing 6 to 22 carbon atoms, R ⁷ is hydrogen or methyl, and R ⁸ is 1 to 4 It is a linear or branched alkyl group containing a carbon atom, and m is a number from 1 to 20. Representative examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid,
Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachinic acid, gadolinic acid, behenic acid and erucic acid methyl, ethyl, propyl, isopropyl, butyl and tert- It is a product in which an average of 1 to 20 mol, preferably 5 to 10 mol, of ethylene and / or propylene oxide are formally inserted into the butyl-esters and their technical mixtures. These products are usually prepared by inserting an alkylene oxide into a carbon ester bond in the presence of a special catalyst (eg, calcined hydrotalcite). Particularly preferred are the reaction products of an average of 5 to 10 moles of ethylene oxide to the ester linkages of industrial coconut oil fatty acid methyl esters. Alkyl oligoglycosides and alkenyl oligoglycosides, which are also suitable nonionic surfactants, usually correspond to the formula (VI):

Embedded image Wherein R ⁹ is an alkyl containing 4 to 22 carbon atoms and / or
Or an alkenyl group, G is a sugar unit containing 5 or 6 carbon atoms, and p is a number from 1 to 10. These can be obtained by suitable manufacturing organic chemical methods. EP-A1 0 301 298 and WO 90/03977 are mentioned as representatives of the extensive literature available on this subject. Alkyl and / or alkenyl oligoglycosides are 5-6
It can be derived from aldoses or ketoses containing carbon atoms, preferably glucose. Thus, suitable alkyl and / or alkenyl oligoglycosides are alkyl and / or alkenyl oligoglucosides. The subscript p in the general formula (VI) is the degree of oligomerization (DP),
That is, it indicates the distribution of monoglycosides and oligoglycosides, and is a number from 1 to 10. P in a given compound must always be an integer and can take, inter alia, values from 1 to 6, but the value p for a particular alkyl oligoglycoside
Is the analytically determined complexity, which is generally a fraction. Alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0 are preferably used. From a practical point of view, alkyl and / or alkenyl oligoglycosides having a degree of oligomerization of less than 1.7, in particular 1.2 to 1.4, are preferred. The alkyl or alkenyl group R ⁹ may be derived from a primary alcohol containing 4 to 11, preferably 8 to 10 carbon atoms. Representative examples are butanol, capron alcohol, caprin alcohol and undecyl alcohol and their industrial mixtures obtained, for example, by hydrogenation of industrial fatty acid methyl esters or aldehydes from Roelen's oxo synthesis. Obtained upon separation by distillation of industrial C _8-18 coconut fatty alcohol as the first fraction may comprise a C ₁₂ alcohol of less than 6% by weight as impurities, alkyl oligoglucosides having a chain length of C ₈ -C ₁₀ ( DP = 1-3) and alkyl oligoglucosides based on industrial C _9/11 oxo alcohols (DP
= 1 to 3) are also suitable. Also, an alkyl or alkenyl group
R ⁹ can also be derived from a primary alcohol containing 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroserinyl alcohol, aralkyl alcohol, gadreyl alcohol, behenyl alcohol, ercil alcohol, brush Zyl alcohols and their industrial mixtures obtained as described above. 1
Alkyl _{oligoglucosides} based on hydrogenated C12 / ₁₄ coconut oil alcohol with a DP of ₃₃ are preferred.

Representative examples of cationic surfactants include, among others:
For example, dimethyl distearyl ammonium chloride,
A tetraalkylammonium compound such as hydroxyethylhydroxycetyldimonium chloride (Dehyquart E (trade name)) and an ester quat. The ester quat is, for example, a quaternized fatty acid triethanolamine ester salt corresponding to formula (VII):

Embedded image Wherein, R ¹⁰ CO is an acyl group containing 6 to 22 carbon atoms, R ¹¹ and R ¹² have the same meaning as either R ¹⁰ CO represents a hydrogen independently of one another, R ¹³ is 1 to 4 Alkyl group or (CH ₂ CH ₂ O) _x4 H group, wherein x1, x2 and x3 are
Means 0 or a number from 1 to 12, x4 is a number from 1 to 12, and Y is a halide, alkyl sulfate or alkyl phosphate. Representative examples of ester quats that can be used in accordance with the present invention include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
It is a product based on isostearic acid, stearic acid, oleic acid, elaidic acid, arachiic acid, behenic acid and erucic acid and their industrial mixtures obtained, for example, by high-pressure hydrolysis of natural fats and oils. And industrial C _12/18 coconut oil fatty acid, especially partially hydrogenated C _16/18 tallow or palm oil fatty acids and high-elaidic C _16/18 fatty acid fraction is preferably used. To make quaternized esters, fatty acids and triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1. Taking into account the performance characteristics of the ester quat, 1.2: 1
A ratio of 2.22.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. Suitable ester quats are 1.
An industrial mixture of monoesters, diesters and triesters with an average degree of esterification of 5-1.9, industrial grade
_{Derived from C16} / ₁₈ tallow or palm oil fatty acids (iodine value 0-40). In terms of performance, a quaternized fatty acid triethanolamine ester salt corresponding to formula (VII)
¹⁰ CO is an acyl group containing 16 to 18 carbon atoms, and R ¹¹
Have the same meaning as R ¹⁰ CO, R ¹² is hydrogen, R ¹³ is a methyl group, x1, x2 and x3 represent 0, and Y represents methyl sulfate. It turns out that there is. Other suitable ester quats other than the quaternized fatty acid triethanolamine ester salt have the formula (VIII)
Is a quaternized ester salt of a fatty acid with a diethanolalkylamine, corresponding to:

Embedded image Wherein R ¹⁴ CO is an acyl group containing 6 to 22 carboxylic acids, R ¹⁵ is hydrogen or has the same meaning as R ¹⁴ CO, and R ¹⁶ and R
¹⁷ is an alkyl group containing 1 to 4 carbon atoms independently of each other, x1 and s2 both represent a number of 0 or 1 to 12, and Y
Represents a halide, an alkyl sulfate or an alkyl phosphate. Finally, another group of suitable ester quats are fatty acids and 1,2-, corresponding to the following formula (IX):
It is a quaternized ester salt with dihydroxypropyldialkylamine:

Embedded imageWhere R¹⁸CO is an acyl group containing 6 to 22 carbon atoms
R¹⁹Is hydrogen or R ¹⁸Has the same meaning as CO, R²⁰, R
^{twenty one}And R^{twenty two}Has 1 to 4 carbon atoms independently of each other
An alkyl group, x1 and x2 are both 0 or a number from 1 to 12.
Where Y is halide, alkyl sulfate or alkyl
Lephosphate means. Finally, other suitable esthetic
Lequats have an ester bond replaced by an amide bond.
And preferably based on diethylenetriamine,
It is a substance corresponding to the formula (X):

Embedded imageWhere R^{twenty three}CO is an acyl group containing 6 to 22 carbon atoms
R^{twenty four}Is hydrogen or R ^{twenty three}Has the same meaning as CO, R^{twenty five}And R
²⁶Is an alkyl group containing 1 to 4 carbon atoms independently of each other
And Y is halide, alkyl sulfate or
Luquil phosphate. Such amide esters
Quotes are, for example, Incroquat® (Croda)
It is commercially available under the name.

As an amphoteric or zwitterionic surfactant, the composition may comprise an alkyl betaine, an alkyl amido betaine, an aminopropionate, an aminoglycinate, an imidazolinium betaine, and / or a sulfobetaine. Examples of suitable alkyl betaines are secondary carboxylation products, especially quaternary amines corresponding to formula (XI).

Embedded image Wherein R ²⁷ is an alkyl containing 6 to 22 carbon atoms and / or
Or represents an alkenyl group, R ²⁸ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ²⁹ represents an alkyl group having 1 to 4 carbon atoms, y1 is a number from 1 to 6 , Z is an alkali metal and / or an alkyl earth metal or ammonium. Representative examples are hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, _{dodecylethylmethylamine} , C12 / ₁₄ cocoalkyldimethylamine, myristyldimethylamine, cetyldimethyl It is the carboxymethylation product of amines, stearyl dimethylamine, stearyl ethyl methylamine, oleyl dimethylamine, _{C16 / 18} tallow alkyl dimethylamine, and technical mixtures thereof. Also suitable are the carboxyalkylated products of amidoamines corresponding to formula (XII).

Embedded image Where R ³⁰ CO is from 6 to 22 carbon atoms and 0 or 1
An aliphatic acyl group containing three double bonds, R ³¹ is hydrogen or
Represents an alkyl group containing from 1 to 4 carbon atoms, R ³² represents an alkyl group containing from 1 to 4 carbon atoms, y ² and y ³
Are independently of each other a number from 1 to 6, and Z is an alkali metal and / or an alkyl earth metal or ammonium. Representative examples are fatty acids containing 6 to 22 carbon atoms, i.e., caproic, caprylic, capric,
Lauric acid, mystic acid, palmitic acid, palmito oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachinic acid, gadolinic acid, behenic acid, elka Of acids and technical mixtures thereof with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminoethylamine, N, N-diethylaminopropylamine condensed with sodium chloroacetate Is the reaction product of Condensation products of sodium chloroacetate and _{C8 / 18} -coco fatty acid-N, N-dimethylaminopropylamide are preferably used.

[0021] Imidazolelinium betaine may also be used. These compositions are compounds obtainable, for example, by cyclocondensation of one or two moles of a fatty acid with polyfunctional amines such as, for example, aminoethylethanolamine (AEEA) or dimethylenetriamine. The corresponding carboxyalkylation product is a mixture of different open-chain betaines. Typical examples are condensation products of AEEA of higher fatty acid, preferably a imidazo over phosphorus emissions such that based on lauric acid or C _12/14 coco fatty acids betainized with sodium chloroacetate subsequently.

Builder The laundry detergent, dishwashing detergent and detergent composition of the present invention comprise:
In addition, inorganic and organic builders can be included.
Suitable inorganic builders are mainly zeolites, crystalline sheet silicates, amorphous silicates and, if acceptable, phosphates such as tripolyphosphates can also be used.

The synthetic zeolite containing microcrystals and bound water that can be used in the present invention is preferably zeolite A and / or P. Commercially available zeolite MAP (registered trademark) (Crosfi
eld) is a particularly suitable zeolite P. However, zeolites X and mixtures of zeolites A, X and / or P are also suitable. Zeolite X and zeolite A
Also suitable for the present invention is a eutectic sodium / potassium aluminosilicate (zeolite X about 80% by weight), which comprises:
For example, commercially available products (VEGOBOND AX (registered trademark), CONDEAAugus
ta S. p. A.).

The zeolites can be used in the form of a spray-dried powder or in the form of an undried stabilized suspension moistened by production. If the zeolite is used in the form of a suspension, the suspension may contain further small amounts of non-ionic surfactants or stabilizers, and as non-ionic surfactants, may contain 1 to 10% by weight of zeolite. 3% by weight of ethoxylated C _{12 ~ 18} fatty alcohols (EO 2 to 5 mol-containing), C _{12 ~ 14} fatty alcohols (EO. 4 to
5 mol) or ethoxylated isotridecanol. Suitable zeolites have an average particle size of less than 10 μm (volume distribution measured by Coulter CounterMethod)
And preferably 18 to 22% by weight, more preferably
It contains 20 to 22% by weight of bound water.

Other suitable layered silicates are disclosed, for example, in DE-B-23 34 899, EP-A-0 026 52
9 and DE-A-35 26 405. The layered silicate is not limited to a specific compositional formula. However, smectites, especially bentonite, are preferred.

A suitable layered silicate belonging to the water-swellable smectite system is represented by the following formula, for example. (OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ Montmorillonite (OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite (OH) ₄ Si _{8- y} Al _y (Mg _6-z Al _z ) O ₂₀ saponite

In the above formula, x = 0-4, y = 0-2 and z = 0-
6 A small amount of iron can be incorporated into the layered silicate crystal lattice of the above formula. In addition, phyllosilicates can have hydrogen, alkali metal and alkaline earth metal ions, especially Na ⁺ and Ca ⁺ , due to their ion exchange properties. The water content of the hydrate is generally between 8 and 20% by weight, depending on the degree of swelling or the treatment method.
Suitable layered silicates are described, for example, in the following documents: US 3,966,629 US 4,062,647, EP 0026529 A1and EP
0028432 A1. Preferably, a layered silicate from which most of the calcium ions have been removed by an alkali treatment can be used.

Another useful builder is the coefficient (Na ₂ O: SiO ₂
Ratio) about 1: 2 to about 1: 3.3, preferably about 1: 2 to 1: 2.8,
More preferably, it is an amorphous sodium silicate having a ratio of about 1: 2 to 1: 2.6, which exhibits multiple wash cycle properties due to delayed dissolution. In the prior art amorphous sodium silicate, delayed dissolution can be obtained in various ways, such as surface treatment, compounding treatment, compression or overdrying. The term "amorphous" as used herein,
X-ray means amorphous. That is, silicates show no sharp X-ray reflections typical of crystalline materials in X-ray diffraction experiments, and at best, the maximum of scattered X-rays with a range of diffraction angles of several degrees. Shows only one or more values. However, particularly good builder properties can be achieved in electron diffraction experiments, even when the silicate particles form a bent or sharp diffraction maximum. This means that the crystallite area of the product is between 10 and several hundred nm in size (up to 50 nm),
The dimensions described are particularly preferred with dimensions up to 20 nm. The so-called X-ray amorphous silicates, which exhibit dissolution characteristics delayed from ordinary water glass, are DE-A
-44 00 024. Compressed amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.

Known phosphates can, of course, be used as builder substances if they are ecologically sound. Suitable phosphate builders are sodium salts such as orthophosphoric acid and pyrophosphoric acid, and particularly preferred phosphate builders are sodium salts of tripolyphosphoric acid. The dose is generally up to 25% by weight, preferably up to 20% by weight, based on the final detergent composition. Optionally, the use of tripolyphosphate, in combination with other builders, especially in small amounts (eg, up to 10% by weight based on the final detergent composition), can provide a synergistic improvement in multiple wash cycle performance. It turned out to be.

Useful organic builders are polycarboxylic acids which are useful, for example, in the form of their sodium salts, provided that they are ecologically safe to use, examples of which are citric acid, adipic acid, succinic acid Acids, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and mixtures thereof. Suitable salts are salts of polycarboxylic acids, examples of carboxylic acids include citric, adipic, succinic, glutaric, tartaric, sugar acids and mixtures thereof.

The above-mentioned acids can be used in the form of an acid. Such acids, besides their builder action, typically exhibit properties as acidifying components and, therefore,
Helps to form relatively low and moderate pH detergents. Particularly suitable acids in this connection are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof.

Other useful organic builders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starch. The hydrolysis can be carried out by a conventional method such as an acid catalyst method or an enzyme catalyst method. The final product is preferably a hydrolysis product with an average molecular weight of 400-500,000. Polysaccharides with a dextrose equivalent (DE) of 0.5 to 40, especially 2 to 30, are preferred. Dextrose equivalent is a measure of the acceptable reducing action of polysaccharides compared to DE 100 dextrose. Maltodextrin with DE 3-20 and DE 2
0-37 dried glucose syrup and average molecular weight 2,000
Relatively high molecular weight yellow and white dextrins of 3030,000 can also be used. Suitable dextrins are the substances described in UK Patent Application 94 19 091 A1. Such an oxidized derivative of dextrin is a reaction product of dextrin and an oxidizing agent, and the oxidizing agent oxidizes at least one alcohol group of the sugar ring to a carboxylic acid. Dextrins oxidized in this way and their preparation are disclosed in the following documents: EP 0 232 202 A1, EP 0 427 349 A1, EP 0 472 042
A1, EP 0 542 496 A1, WO 92/18542, WO 93/08251, WO
93/16110, WO 94/28030, WO 95/07303, WO 95/12619,
WO 95/20608. The oxidized polysaccharides described in DE 196 00 018 A1 are also
It is suitable. Products oxidized at the 6-position carbon of the sugar ring are particularly preferred.

Cobuilders Other suitable cobuilders are oxydisuccinates and their derivatives, preferably ethylenediaminedisuccinate. In this connection, glycerol disuccinates and glycerol trisuccinates described in the literature are particularly suitable: US 4,524,009, US 4,639,325, EP 0
150 930 A1 and JP 93/339896. Zeolite and / or
Alternatively, the dose of the silicate-containing composition is 3-15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids and their salts, which may be present in lactone form, comprising at least 4 carbon atoms, at least one hydroxy group and at most 2 Contains acidic groups. These cobuilders are, for example, WO 9
5/20029.

Suitable polycarboxylate polymers are
For example, the sodium salt of polyacrylic acid or polymethacrylic acid, for example, having a relative molecular weight of 800 to 150,000 (acid basis, measured with respect to polystyrene sulfonic acid). Suitable polycarboxylate copolymers are in particular copolymers of acrylic acid and methacrylic acid and copolymers of acrylic acid or methacrylic acid and maleic acid. Particularly preferred acrylic / maleic acid copolymers have been found to be copolymers of 50-90% by weight acrylic acid and 50-10% by weight maleic acid. Its relative molecular weight is generally from 5,000 to 200,000, preferably from 10,000 to 12, based on the free acid.
0,000, more preferably 50,000-100,000 (measured against polystyrene sulfonic acid).

The carboxylate (co) polymer poly is
It can be used in either powder or aqueous form. A 20-55% by weight aqueous solution is preferred. Granular polymers are generally added in one or more subsequent steps to one or more types of basic granules. Also, particularly preferably, biodegradable polymers consisting of two or more different monomer units, for example salts of acrylic acid and maleic acid, and substances containing vinyl alcohol or derivatives thereof as monomers (DE-A1-43 00 772), Or acrylic acid and 2
-A substance (DE-C2-42 21 381) containing a salt of an alkylarylsulfonic acid and a saccharide derivative as a monomer.
Other suitable copolymers are DE-A1-43 03 320 and DE-A1
-44 17 734, which preferably comprises acrolein and acrylic acid / salt thereof, or acrolein and vinyl acetate as monomers. Other suitable builders are aminocarboxylic acid polymers, salts and precursors thereof. Polyaspartic acid and its salts and derivatives are particularly preferred.

Another suitable builder is polyacetal, which can be obtained by reacting a dialdehyde with a polyol carboxylic acid (5-7 carbon atoms and at least 3 hydroxy groups) (EP-A1). -0 280 22
3). Suitable polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and polyol carboxylic acids such as gluconic acid and / or glucoheptanoic acid.

Grease-Removing Component The composition of the present invention may further contain a component that promotes the removal of grease from textiles by washing. Suitable oil-removing components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose (15-30% by weight of methoxy groups and 1-15% by weight, respectively, based on the amount of nonionic cellulose ether). Hydroxypropyl groups) and known phthalic acid and / or terephthalic acid polymers and their derivatives, especially polymers of ethylene terephthalate and / or polyethylene glycol terephthalate and their anionic and / or
Alternatively, a nonionic modified derivative is exemplified. Of these, sulphonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Water-Soluble Inorganic Salts Other ingredients suitable for the detergents of the present invention include water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, ordinary water which does not exhibit any great builder properties. Glass or a mixture thereof. Alkali metal carbonates and amorphous alkali metal silicates, especially Na ₂ O: SiO ₂ molar ratios of 1: 1 to
Sodium silicate, which is 1: 4.5 (preferably 1: 2 to 1: 3.5) is particularly preferred. The sodium carbonate content in the final composition is suitably up to 40% by weight, in particular 2-35% by weight. When sodium silicate is not used as a builder, its content in the detergent is usually up to 10% by weight, preferably
1 to 8% by weight.

Other Detergent Components In addition to the components described above, the detergent compositions of the present invention can include other conventional additives. For example, polyphosphonic acid, a fluorescent brightener, an enzyme, an enzyme stabilizer, a small amount of a neutral salt of a filler, a dye, a fragrance and the like are exemplified.

Bleaching agents Of the bleaching compounds that produce hydrogen peroxide (H ₂ O ₂ ) in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. . Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrate-forming or hydrogen peroxide-forming persalts or peracids, such as perbenzoates, peroxophthalates Acid salts, diperazelinic acid, phthaliminoperacid or diperdecanedioic acid. The content of peroxy bleach in the composition is preferably 5-35% by weight, preferably up to 30% by weight, and perborate monohydrate or percarbonate is advantageously used. .

Bleaching activators Suitable bleaching activators are perhydrolysis.
Under conditions, aliphatic peroxocarboxylic acids, preferably C _{1 to
10} (preferably C _{2 ~ 4)} is a compound such as to form an aliphatic peroxocarboxylic acids and / or unsubstituted or substituted perbenzoic acid. O- and / or having the above number of carbon atoms
Or substances containing N-acyl groups and / or unsubstituted or substituted benzoyl groups are preferred. Suitable bleach activators include polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) ), Acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols,
Especially triacetin, ethylene glycol diacetate,
And 2,5-diacetoxy-2,5-hydrofuran and enol esters (DE 196 16 693 A1 and DE 196 16 76
7 A1), acetylated sorbitol, mannitol and mixtures thereof (EP 0 525 239 A1, SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG),
Pentaacetylfructose, tetraacetylxylose and octaacetyllactose, acetylated (optionally N-alkylated) glucamine and gluconolactone and / or N-acylated lactams, for example N-benzoylcaprolactam (WO94 / 27970, WO94 / 28102) , WO
94/28103, WO95 / 00626, WO95 / 14759 and WO95 / 174
98). It is also preferred to use hydrophilic substituted acylacetals (DE 196 16 769 A1) and acyl lactams (German patent applications DE 196 16 770 and WO 95/14075). Also the customary bleach activator combinations (DE 44 43 177) can be used. Such bleach activators are used in conventional amounts, preferably 1 to 10% by weight, more preferably 2 to 8% by weight, based on the total detergent / detergent.

Bleaching Catalyst In addition to or instead of the conventional bleach activators described above, sulfonimides (EP 0 446 982 B1, EP 0 453 003)
B1) and / or bleach-promoting transition metal salts or transition metal complexes can be used as so-called bleach catalysts. Suitable transition metal compounds include, in particular, the following substances: manganese-, iron according to DE 195 29 905 A1
-, Cobalt-, ruthenium- or molybdenum-selenium complexes and their N-analogs (DE 196 20 267 A1),
Manganese-, iron-, cobalt-according to DE 195 36 082 A1,
Ruthenium- or molybdenum-carbonyl complexes, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes, such as those containing a nitrogen-containing tripod ligand according to German Patent Application DE 196 05 688, DE 196 20
Cobalt-, iron-, copper- and ruthenium-ammine complexes according to 411 A1, manganese, copper and cobalt complexes according to DE 44 16438 A1, cobalt complexes according to EP 0 272 030 A1, E
Manganese complexes described in P 0 693 550 A1, European Patent EP 0 392
Manganese, iron, cobalt and copper complexes according to 592 A1,
European patent EP 0 443 651 or European patent application EP 0 458 397
A1, EP 0 458 398 A1, EP 0 549 271 A1, EP 0 549 27
2 A1, a manganese complex according to EP 0 544 490 A1 and EP 0 544 519 A1. Combinations of bleach activators with transition metal bleach catalysts are known, for example, from DE 196 13 103 A1 and WO 95/27775. Preferably, a bleach-enhancing transition metal complex having manganese, iron, cobalt, copper, molybdenum, vanadium, titanium and / or rubidium as central atom is used, the dosage of which is based on the total detergent / cleaning agent, Preferably 0.0025 to 0.25% by weight, more preferably 0.01 to
0.1% by weight.

Enzymes Suitable enzymes are, in particular, proteolytic enzymes (proteases), esterolytic enzymes (esterases), lipases or lipolytic enzymes, starch hydrolases (amylases), cellulases or other glycosyl hydrolases and mixtures thereof. Such enzymes are from the class of hydrolases. All of these hydrolases contribute to the removal of stains and discolorations, such as protein-, fat- or starch-containing stains, by washing. Cellulases and other glycosyl hydrolases can contribute for color retention and to increase fiber flexibility by removing pilling and microfibers. Oxidoreductases may also be used to bleach and to inhibit dye transfer. Bacterial species such as Bacillus Subtilis, Bacillus licheniformis, Streptomyces gtiseus and Humicola insolens;
Enzymes obtained from fungi are particularly suitable. Subtilis type proteases are preferably used, with proteases obtained from Bacillus lentus being particularly preferred. Particular objects in this connection are, for example, proteases and amylases, or proteases and lipases, or lipolytic enzymes or proteases and cellulases, or cellulases and lipases or lipolytic enzymes, or proteases, amylases and lipases or lipolytic enzymes or proteases, It is an enzyme mixture of lipase or lipolytic enzyme and cellulase, but especially a protease- and / or lipase-containing mixture or a mixture with lipolytic enzymes. An example of such a lipolytic enzyme is the known chitinase. Peroxidases (peroxidases) and oxidases (oxidases) have also been usefully used in some cases. Suitable amylases include, inter alia, α-amylases, isoamylases, planases, pectinases. Preferred cellulases are cellobiohydrolases, endoglucanases, and β-glucosidases (also called cellobiases), and mixtures thereof. Cellulase has different CMCase and avicelase activities depending on its type,
The desired activity can be achieved by mixing the cellulases in a suitable ratio. The enzyme can be adsorbed on a carrier material or embedded in an envelope material to protect the enzyme from premature degradation. The content of enzyme, enzyme mixture or enzyme granules is preferably about 0.1-5% by weight,
More preferably, it may be about 0.12 to 2% by weight.

Enzyme Stabilizers In addition to monohydric and polyhydric alcohols, the compositions of the present invention may include other enzyme stabilizers. For example, 0.5
To 1% by weight of sodium formate may be used. Stabilized with a water-soluble calcium salt, preferably about 1.2
Proteases having a calcium content of% by weight may also be used. In addition to calcium salts, magnesium salts also serve as stabilizers. However, for example,
Orthoboric acid (H ₃ BO _3), boric acid, such as metaboric acid (HBO _2), and pyroborate (tetraborate H ₂ B ₄ O _7), boron oxide, borax and other borate alkali metal salt It is particularly advantageous to use boric compounds.

The function of redeposition inhibitors redeposition agents, soil away from the fibers kept suspended in the washing liquid, is that thereby preventing dirt from being re-absorbed by the laundry. Suitable redeposition inhibitors include polymeric carboxylic acids, guar, water soluble salts of gelatin,
It is a water-soluble, usually organic colloid, such as a carboxylic or ether ether of starch or cellulose, or an acidic sulfate ether of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch compositions and other starch products, such as starch degradation products, aldehyde starch, and the like, may be used. Polyvinyl pyrrolidone is also suitable. Cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose,
It is also suitable to use hydroxyalkylcellulose, mixed ethers (for example methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose), and mixtures thereof, and polyvinylpyrrolidone, for example, in an amount of 0.1 to 5% by weight, based on the detergent. It is.

Fluorescent Whitening Agent The detergent of the present invention can contain a derivative of diaminostilbene disulfonic acid or an alkali metal salt thereof as a fluorescent whitening agent. Suitable optical brighteners are, for example, 4,
4'-bis- (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid salt or a similar structure, in place of the morpholino group, It is a compound having a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Substituted diphenylstyryl type brighteners can also be used, for example, 4,4'-bis- (2-sulfostyryl) diphenyl, 4,4'-bis- (4-
Examples are the alkali metal salts of chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4 ′-(2-sulfostyryl) diphenyl. Mixtures of the above brighteners can also be used. For example, between 0.1 and 0.5% by weight,
Suitably, in addition to a conventional optical brightener in a conventional amount, preferably between 0.1 and 0.3% by weight, the composition is for example 10 ^-6 to 10 ^-3 % by weight,
If it also contains a small amount of blue dye, preferably around ^10-5 % by weight,
Uniform white granules are obtained. Particularly suitable dyes are (Ciba-
Tinolux® (a product of Geigy).

Soil Release Agents Suitable soil release agents are ethylene terephthalate and / or
Alternatively, it is a substance which preferably contains a polyethylene glycol terephthalate unit and has a molar ratio of ethylene terephthalate / polyethylene glycol terephthalate in the range of 50:50 to 90:10. More preferably, the molecular weight of the polyethylene glycol linking unit is in the range of 750 to 5,000, ie, the degree of ethoxylation of the polymer containing the polyethylene glycol unit may be about 15 to 100. The polymers are characterized by an average molecular weight of about 5,000 to 200,000 and may have a block structure, but preferably have a random structure. Preferred polymers have a molar ratio of ethylene terephthalate: polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30
It's like a range of 80:20. Other suitable polymers include polyethylene glycol linking units having molecular weights ranging from 750 to 5,000, preferably from 1,000 to about 3,000, and have a molecular weight of about 10,000 to about 50,000 of the polymer. Is what you have. An example of a commercially available polymer is the product Mi
lease (registered trademark) T (ICI) or Repelotex (registered trademark) SRP3 (Rhone-Poulenc).

The disintegrant solid composition may further comprise a disintegrant. Disintegrants are substances that are added to a molded body to promote its disintegration when it comes into contact with water. Disintegrants are described, for example, in J. Phar
m.Sci.61 (9172), and Rompp Chemielexikon, 9th E
dition, Vol. 6, page 4440. The disintegrant forms a concentrated portion increased by its production when observed under a microscope, but may be homogeneously dispersed in the molded article when viewed with the naked eye. Suitable disintegrants include, for example, native starch and its derivatives (carboxymethyl starch,
Starch glycolate, agar agar, guar gum, guar gum, pectin, etc. in the form of alkali metal salts, cellulose and its derivatives (carboxymethylcellulose, microcrystalline cellulose), polyvinylpyrrolidone, collodion, arginic acid and its alkali metal salts, amorphous Or partially crystalline layered silicate (bentonite),
Includes polysaccharides such as polyurethanes, polyethylene glycols and blowing agent systems. Other examples of disintegrants that may be present in connection with the present invention are, for example, patents WO98 / 40462 (Rettenmaier), WO98 / 55583 and WO98 / 5559.
No. 0 (Unilever) and WO98 / 40463, DE19709991
And DE19710254 (Henkel).
These disclosures will be described in this specification. The shaped body is present in an amount of from 0.1 to 25% by weight, preferably from 1 to 25% by weight, based on the shaped body.
The disintegrant may be included in an amount of 20% by weight, more preferably 5 to 15% by weight.

Perfume Suitable perfume oils or perfumes include perfuming compounds such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbon-based compounds. Representative of ester-based flavoring compounds are benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate , Allylcyclohexyl propionate, styralyl propionate and benzyl salicylate. Benzyl ethyl ether is exemplified as an ether-based flavoring compound. As perfuming compounds of the aldehyde, the linear alkanals of C _{8 ~ 18,} citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy citronellal, lilial and bourgeonal, and the like. Suitable ketone-based compounds are ionone, α-isomethylionone, and methylseryl ketone. Examples of alcohol compounds include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, terpineol, and the like. Examples of the hydrocarbon compound include terpenes such as limonene and pinene. Preferably, however, a mixture of different fragrances is used, which together produce an attractive aroma. Such perfume oils can include natural flavor mixtures such as those obtained from plant sources, examples of which include pine oil, citrus oil, jasmine oil, patchouli oil, rose oil, ylang ylang oil and the like. . Preferred are sage oil, chamomile oil, clove oil, balsam oil, mint oil, cinnamon oil, lime-blossom oil, juniper berry oil, vetiver oil, olive oil, galvanum oil, labodanum oil, orange brossam oil , Neroli oil, orange peel oil, sandalwood oil and the like.

Perfumes can be directly incorporated into the tablets of the present invention. In another advantageous embodiment, the fragrance is applied to a carrier that enhances the attachment of the fragrance to the laundry, and the slow release of the fragrance ensures long-lasting perfume on the laundry. An example of a suitable carrier material is cyclodextrin, where cyclodextrin /
The perfume complex can optionally be coated with other auxiliaries.

Fillers If desired, the final composition may further comprise an inorganic salt such as, for example, sodium phosphate as a filler, preferably in an amount of from 0 to 10% by weight, more preferably of 1 to 10% by weight, based on the composition. To 5% by weight.

Preparation of Compositions The compositions available using the new regulated foam granules may be prepared and used in the form of powders, extrudates, granules or agglomerates. These may be both heavy duty and light duty detergents in small or micro form, if desired, or detergents for colored fibers, if desired. Such compositions may be manufactured by any relevant process known in the art. They are preferably made by mixing together various particle compositions, including detergent components. The particle composition may be prepared by spray drying, simple mixing or a complex granulation process such as, for example, fluid bed granulation. In one particularly preferred embodiment, at least one surfactant-containing composition is produced by fluid bed granulation.
In another particularly preferred embodiment, the aqueous composition of the alkali metal silicate and the alkali metal carbonate is sprayed into a dryer together with other detergent components, and drying is optionally carried out by granulation.

[0054] If the dryer dryer capable of spraying an aqueous composition may be any type of dryer. According to one preferred embodiment of the process, the drying is performed by spray drying in a drying tower. In this case, the aqueous composition is exposed in a conventional manner to a stream of dry gas in good particulate form. Applicants describe embodiments of spray drying with excess hot air in several issued patents. The principles of operation disclosed in these publications are specifically included herein as part of the disclosure of the present invention. References are in particular the following publications: Patent No.DE40
30 688 A1 and further below DE 42 04 035 A1,
DE42 04 090 A1, DE 42 06 050 A1, DE 42 0
6 521 A1, DE 42 06 495 A1, DE 42 08 773 A1
No. DE 42 09 432 A1, DE 42 34 376 A1.

According to another preferred variant, especially if a high bulk density detergent is obtained, the mixture is then subjected to a compression step, and the other ingredients are added to the detergent after this compression step. In one preferred embodiment of the present invention, the components are compressed by a compression agglomeration method. The compression agglomeration method, in which the solid premix (dry base detergent) is processed, can be performed by various aggregators. Classified according to the type of coagulator used. The four most common compression agglomeration methods suitable for the purposes of the present invention are extrusion, roll compression, pelletizing, and tableting, and the preferred agglomeration processes for the purposes of the present invention are extrusion, roll Compression, pelletization and tableting.

As described above, common to all four processing methods is 1
One feature is that the premix is compressed under pressure to plasticize, compressing the individual particles together to reduce porosity and adhere the particles together. In all processing steps (but with certain limitations in the tableting process), the components of the compression agglomeration device can be heated to a relatively high temperature, and the heat generated by the shearing force can be cooled and released. Can be.

In all methods, one or more binders may be used as compression aids. However, it has to be clarified in this case that, in principle, any number of different binders and mixtures of different binders may be used. A preferred embodiment of the present invention is:
It is characterized by the use of a binder which is completely in the form of a melt at a temperature of at most 130 ° C., preferably at most 100 ° C., more preferably only up to 90 ° C. In other words, the binder must be selected according to the method and the processing conditions, or the processing conditions and, in particular, the processing temperature must be adapted to the binder if a specific binder is to be used.

The actual compression step is preferably carried out at least at a processing temperature corresponding to the softening or melting point of the binder. According to a preferred embodiment of the present invention, the processing temperature is substantially higher than the melting point or substantially higher than the temperature at which the binder is present as a melt. However, according to one particularly preferred embodiment of the invention, the processing temperature of the compression step is at most 20 ° C. above the melting temperature of the binder or the upper limit of the melting temperature range. Technically, higher temperatures can be applied, but a temperature difference to the melting or softening temperature of the binder of 20 ° C. is generally sufficient, higher temperatures do not provide additional benefits. It has been found. Therefore, particularly preferably, in terms of energy, the melting point of the binder or preferably a temperature higher than the upper limit temperature of the melting range, but the compression treatment is performed at a temperature as close as possible to the melting point or the upper limit temperature. . Controlling the temperature in this manner has the following additional advantages. That is, temperature-sensitive raw materials such as peroxy bleach, such as perborate and / or percarbonate, and enzymes can be actively treated without significant loss of their active substances. The ability to control the temperature of the binder in a particularly important compression step (ie between the premix mixing / homogenization step and the molding step) makes the process of the invention very good in terms of energy consumption. And it can be carried out without damaging the heat-sensitive components in the premix. This is because the premix is exposed to relatively high temperatures for only a short time. According to the preferred compression agglomeration step of the present invention, the temperature of the processing components of the compression agglomeration apparatus (for example, the screw of the extruder, the roll of the roll compressor and the roll of the pellet press) is preferably up to 150 ° C. Is up to 100 ° C., more preferably up to 75 ° C., and the processing temperature is at most 30 ° C., especially at most 20 ° C. above the melting temperature of the binder or the upper limit of the melting temperature range. According to a preferred embodiment of the present invention, the heat exposure time in the compression zone of the compression agglomeration device is up to 2 minutes,
Preferably, it is 30 seconds to 1 minute.

Suitable binders which may be used in the form of the binder alone or in a mixture with other binders are polyethylene glycol,
1,2-polypropylene glycol and modified polyethylene glycol and polypropylene glycol.
For modified polyalkylene glycerol, especially 600 to 1
Included are polyethylene glycol or polypropylene glycol sulfates and / or disulfates having a relative molecular weight of up to 2,000, more preferably from 1,000 to 4,000. Other groups have their own
Mono-polyalkylene glycols having a relative molecular weight ranging from 600 to 6,000, preferably from 1,000 to 4,000.
And / or disuccinate. A more detailed description of modified polyalkylene glycol ethers can be found in the disclosure of International Patent Specification No. WO 93/02176. In the present invention, polyethylene glycol includes polymers produced using _C3-5 glycerol or glycerol and mixtures thereof in addition to ethylene glycol as a starting molecule. In addition, these also
Also include ethoxylation derivatives such as trimethylolpropane with an EO of from 30 to 30. Preferably used polyethylene glycol may have a linear or branched structure, and linear polyethylene glycol is particularly preferred. Particularly preferred polyethylene glycols include those having a relative molecular weight in the range of 2,000 to 12,000, conveniently near 4,000. Polyethylene glycol having a relative molecular weight of less than or equal to 3,500 and of more than 5,000, especially
It may be used in combination with polyethylene glycol having a relative molecular weight around. 50% by weight or more based on the total amount of polyethylene glycol in such a combination is
Conveniently comprises polyethylene glycol having a relative molecular weight of 3,500 to 5,000. However, polyethylene glycol which is present as a liquid at essentially room temperature / 1 bar pressure, in particular all polyethylene glycols having a relative molecular weight of 200, 400 and 600, may also be used as binder. However, these essentially liquid polyethylene glycols should only be used in the form of a mixture with at least one other binder, which mixture must also satisfy the need according to the invention, i.e. It must have a melting or softening point of at least 45 ° C. Other suitable binders are low molecular weight polyvinylpyrrolidone and derivatives thereof with a relative molecular weight of at most up to 30,000. 3,0
Relative molecular weights ranging from 00 to 30,000, for example, around 10,000 are preferred. Polyvinylpyrrolidone is preferably not used as a sole binder, but is used in combination with other binders, more particularly in combination with polyethylene glycol.

Immediately after being discharged from the manufacturing apparatus, the temperature of the compressed substance is preferably a temperature of 60 ° C. or less, more preferably 35 to 65 ° C.
Temperature. It has proven to be particularly advantageous for the temperature of the discharged material, in particular the temperature of the material discharged from the extrusion process, to be between 40 and 55 ° C.

According to a preferred embodiment of the present invention, the process of the present invention can be carried out by an extrusion method described in the following literature: EP-B-0 486 592 (Henkel KGa
A), WO-A-93 / 02176 (Henkel KGaA), WO-A-94 / 09111
(Henkel KGaA)). In this extrusion molding step, a solid premix is extruded under pressure to form a strand, and after discharging from a porous die of an extruder head, the strand is pulverized by a cutting device to form granules. The homogeneous solid premix contains a plasticizer and / or a lubricant. These plasticizers and / or lubricants act to soften the premix under pressure or under the conditions of a specific energy application so that the premix can be extruded. Suitable plasticizers and / or lubricants are surfactants and / or polymers.

For the extrusion method, reference is made to the disclosures of the aforementioned patents and patent applications. According to one preferred embodiment of the invention, the premix is preferably fed to a co-rotating or counter-rotating twin-screw extruder. In this case, the housing and the extruder granulation head can be heated to a predetermined extrusion temperature. The premix is at a given pressure (preferably at least 25 bar, but may be less than this level at very high processing speeds, depending on the equipment used) due to the shearing action of the extruder screw. It is compressed, plasticized and extruded through the die plate of the extruder head in the form of fine strands. The extrudate is finally ground with a rotary guillotine knife to suitably form substantially spherical or cylindrical granules. The diameter of the die opening and the length of the strands are chosen according to the dimensions of the selected granules. According to this embodiment, granules having a substantially constant and predetermined particle size can be produced, and the absolute particle size of each particle can be adjusted for the intended purpose of use. Generally, a maximum particle size of 0.8 cm is preferred. According to a preferred embodiment, uniform particles in the mm range can be produced, for example, having a particle size of 0.5 to 5 mm, especially about 0.8 to 3 mm. In this regard,
The length / diameter ratio for the cut primary granules of this embodiment is from about 1: 1 to about 3: 1. Further, preferably, the elastic primary granules are sent to an additional forming step, during which the edges present in the crude extrudate are rounded,
Finally, spherical or nearly spherical extrudate granules can be obtained. If desired, a small amount of desiccant powder, such as zeolite powder, such as zeolite NaA, can be used simultaneously at this stage. The forming process can be performed by a commercially available rounding device. In this connection, care should be taken at this stage to make only a small amount of the fine particle fraction. However, the drying treatment, as disclosed as a preferred specific example in the prior art document, may be performed in a subsequent step, but is not absolutely necessary. Preferably, after the compression step, drying is
Not performed.

As an alternative, the extrusion / pressing step may also be carried out on a low-pressure extruder such as a Kahl press (manufacturer: Amandus Kahl) or a so-called Bextruder (manufacturer: Bepex). In one particularly preferred embodiment of the invention, the temperature prevailing in the moving part of the screw, the pre-dispersing machine and the extrusion die at least reaches and preferably exceeds the melting point of the binder or rather the upper limit of the melting point of the binder. Is controlled. The temperature exposure time in the pressurized part of the extruder is preferably less than 2 minutes,
More particularly between 30 seconds and 1 minute.

According to a preferred embodiment of the present invention, the method of the present invention can be carried out by a roll compression method.
According to this method, a solid premix containing a perfume but substantially free of water is introduced between two rolls (leveling roll or roll with a recessed surface for shaping) and A compression roll process is performed between the rolls to form a compressed material in sheet form. The rolls compress linearly and strongly against the premix and can be heated or cooled as needed. When a leveling roll is used, a smooth compressed sheet having no pattern can be obtained. In contrast, when a patterned roll is used, it is possible, for example, to obtain a patterned compact that can pre-form certain forms on the detergent particles. The sheet compact is then broken by a chopper or crusher to form small pieces,
This can be processed to form granules, and the granules can be further processed, but in particular, the granules can be converted to substantially spherical granules by known surface treatment methods.

According to the roll compression method, the temperature of the component for compression, ie, the temperature of the roll, is at most 150 ° C., preferably at most 100 ° C., more preferably at most 75 ° C. According to one preferred embodiment of the roll compaction process, the processing temperature is a temperature at most 10 ° C., especially at most 5 ° C. above the melting temperature of the binder or the upper limit of the melting temperature range. Heat exposure time in the compression zone of rolls (leveling rolls or rolls with recessed surfaces for shaping) can be up to 2 minutes,
Preferably, it is 30 seconds to 1 minute.

According to a preferred embodiment of the present invention, the method of the present invention can be carried out by a pelletizing method. In this way, a solid premix containing perfume but substantially free of water can be applied to the perforated surface and forced through a perforation by a press roll while at the same time plasticizing. According to the prior art pellet pressing method, the premix is pressed and compressed by a rotating roll, plasticized, pressed into the perforated surface in the form of a strand, and finally ground by a cutting device. The press roll and the perforated surface can assume a number of forms. For example, a flat perforated plate is used as a concave or convex ring die and the material is passed through this die and compressed by one or more press rolls. According to the perforated plate press, the press roll is:
It may be in the form of a cone. According to the ring die press, the die and the press roll can rotate in the same or opposite directions. Suitable presses for carrying out the method according to the invention are described, for example, in the following patent documents: DE-O
S 38 16 842 (Schlueter GmbH). According to the description of this patent document, a ring die press is provided with a rotary ring having a press through hole and at least one cooperatively connected inner surface.
And two press rolls. The material sent to the die space through the press through hole is compressed by the press roll and sent to the discharge device. The ring die and press roll are designed to drive in the same direction, which allows the shear load applied to the premix, and therefore,
Premix temperature increase is reduced. However, the pelletizing process can, of course, be carried out on rolls that can be heated or cooled, and the premix can be adjusted to a predetermined temperature.

Also in this pelletizing method, the temperature of the component for compression, that is, the temperature of the press roll is at most 150 ° C., preferably at most 100 ° C., more preferably at most 75 ° C. According to one preferred embodiment of the pelletizing method, the processing temperature is a temperature at most 10 ° C., especially at most 5 ° C. above the melting temperature of the binder or the upper limit of the melting temperature range.

The preparation in the form of shaped bodies, preferably tablets, comprises:
Generally, it is performed by tableting or compression agglomeration. The specific compression agglomerate obtained may be used directly as a detergent or may be pre-treated in a conventional manner. Conventional post-treatments include, for example, pulverizing with a particulate detergent component that generally provides an increase in bulk density. However, other suitable work-ups are described in DE 195 24 287 A1 and DE 195 47 457
A1. The method according to A1, wherein according to this method, dust-like or at least fine particle components (so-called fine particle components)
Attached to the final particulate product produced according to the invention used as a core. This forms a detergent containing so-called particulate components as the outer shell. Advantageously, this is also done by melt agglomeration. DE-A-195 24 287 A1 for the purpose of melt agglomeration of particulate components
And the disclosure of DE-A-195 47 457 A1 is of particular reference. In a preferred embodiment of the present invention, the solid detergent is in tablet form, the tablet preferably having rounded corners and edges, especially from the point of view of safe storage and transport.
The base of the tablet may be, for example, round or rectangular. Multilayer tablets, especially tablets having two or three layers, which may have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. Tablets may also have compressed and uncompressed portions. If, before compression, particles having a granule component in the diameter range of 0.02 to 6 mm are included in an amount of less than 20% by weight, preferably less than 10% by weight, molded bodies with particularly advantageous dissolution rates are obtained. Particle size distribution from 0.05 to 2.0 mm is preferred, 0.2
A particle size distribution of from 1 to 1.0 mm is particularly preferred.

[0069] EXAMPLE wax-like system prepared in Example 1 10,000 kg aqueous slurry (0.5 wt% of the cellulose ether +5.0 wt% of sodium sulphate, sodium silicate Tasu20.7 wt% of the intermediate product comprising a foaming agent + 15.8% by weight of sodium carbonate + 2.0% by weight of polyacrylate / polymethacrylate + 50% by weight
Water and 6% by weight paraffin wax mixture (freezing point 62
30% by weight of paraffin at ~ 90 ° C + 30% by weight of solid paraffin with a freezing point of 42 to 56 ° C + Liquid paraffin 30 with a freezing point of 35 to 40 ° C
Wt%)) pressure on the dry spray tower by continuous homogenization
Sprayed at 40 bar and dried by a countercurrent flow of hot combustion gas (annular channel temperature 250 ° C. and tower outlet temperature 98 ° C.).

Example 2 10,000 kg of aqueous slurry (0.5% by weight of cellulose ether + 2.0% by weight of sodium silicate + 23.5% by weight of zeolite + 2.0% by weight of polyacrylate / polymethacrylate + 50% by weight of water And 7% by weight of paraffin (freezing point 62-90 ° C.) + 2% by weight of bisstearylethylenediamine were sprayed onto the drying spray tower by continuous homogenization at a pressure of 40 bar and dried by a countercurrent flow of hot combustion gas ( Annular channel temperature 250 ° C and tower outlet temperature 98 ° C).

Preparation of Aqueous Silicone Emulsion Example 3 2,000 kg of a 3.7% by weight aqueous solution (a thickener mixture of sodium carboxymethylcellulose and methylcellulose in a weight ratio of 70:30) were swollen at 25 ° C. for 4 hours. To the resulting solution was added 20% by weight of a polysiloxane antifoam (polydimethylsiloxane containing microcrystalline silanized silica). A stable aqueous emulsion was obtained.

Example 4 2,000 kg of a 3.7% by weight aqueous solution (a thickener mixture of sodium carboxymethylcellulose and methylcellulose in a weight ratio of 70:30) was swollen at 25 ° C. for 4 hours. To the resulting solution was added 30% by weight of corn starch and 20% by weight of a polysiloxane antifoam (polydimethylsiloxane containing microcrystalline silanized silica). A stable aqueous emulsion was obtained.

Fluid bed granulation Example 5 At a rate of 650 kg / h, the powdered intermediate product prepared in Example 1 was passed through a solids metering system via a fluid bed granulator (SKET) equipped with a circular diffuser plate. (Granulator). In addition, dry air at a temperature of 140 ° C is flowed through a circular diffuser plate at a flow rate of about 20,000.
Flowed in at m ³ / h. At a rate of 350 kg / h, the aqueous silicone emulsion prepared in Example 3 was sprayed continuously onto the intermediate product in powder form. The fluidized bed temperature above the diffuser plate is 85 ° C, while the air outlet temperature is
79 ° C. A granule of the following composition was obtained: 7% by weight of silicone, 2.2% by weight of cellulose ether, 9.2% by weight of sodium silicate, 38.0% by weight of sodium sulphate, 29.1
Wt% sodium carbonate, 3.7 wt% polyacrylate / polymethacrylate and 11.0 wt% paraffin wax mixture (30 wt% paraffin with freezing point 62-90 ° C + 30 wt% solid paraffin with freezing point 42-56 ° C + freezing point 35- 40
Liquid paraffin at 30 ° C). The resulting antifoam granules have a bulk density of 810 g / l and a particle size distribution in which the average particle size of 95% by weight of the particles is less than 1.5 mm. The product has very good flowability and does not contain any dust.

Example 6 According to the method of Example 5, the intermediate product in powder form prepared in Example 2 at a rate of 650 kg / h was passed through a solids metering system via a fluidized bed granulator (SKET granulator).
Introduced within. In addition, dry air at a temperature of 100 °
000 m ³ / h. Example 4 at a rate of 350 kg / hr
Was sprayed continuously onto the intermediate product in powder form. The fluidized bed temperature above the diffuser plate is 65 ° C, while the air outlet temperature is 60 ° C. Granules of the following composition were obtained: 7% by weight of silicone, 10.3% by weight of starch, 2.1% by weight of cellulose ether, 3.2% by weight of sodium silicate, 21.2.
Wt% sodium sulfate, 38.1 wt% zeolite, 3.
3% by weight of polyacrylate / polymethacrylate, 11.
5% by weight of paraffin and 3.3% by weight of bis-stearylethylenediamine. The resulting antifoam granules have a bulk density
780 g / l and 95% by weight of the particles have an average particle size of 1.5
It has a particle size distribution that is less than mm. The product has very good flowability and does not contain any dust.

Property Test The prepared antifoam granules are used in an amount of 1.5% by weight of a heavy-duty detergent composition in powder form (8% by weight of sodium alkylbenzenesulfonate + 10% by weight of alkyl ethoxylate + 1.5% by weight). Soap + 10% by weight sodium carbonate + 20% by weight zeolite, 3% by weight sodium silicate, 20% by weight sodium perborate + 2% by weight tetraacetylethylenediamine (TAED) + 0.5% by weight proteolytic enzyme + 100% Up to sodium sulfate and water)
Mix simply by mixing inside. The resulting detergent is
At both 30 ° C and 40 ° C and 60 ° C and 95 ° C,
Satisfactory foam formation behavior was shown.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/32 C11D 3/32 3/382 3/382 17/06 17/06 17/06 (72) Inventor Michael Neuss Germany Day 50997 Cologne, Seezamstrasse 2 (72) Inventor Detlef Stanilovski Germany Day 40822 Mettmann, Düsselring 16 (72) Inventor Karin Koren Germany 40-40227 Düssel Dorf, Heppenheimer Weg No. 18 (72) Inventor Andrea Borntlegger Federal Republic of Germany Day-52781 Hahn, de Rosselweg No. 5 (72) Inventor Bernd Fabry Federal Republic of Germany Day 41352 Korschen-Bloich, Danzi Over Strasse # 31

Claims (14)

[Claims] An antifoam granule for a solid laundry detergent, dishwashing detergent and cleaning composition comprising a carrier material and silicone, wherein the antifoam granule comprises a silicone in an aqueous emulsion form and a carrier material. Characterized in that it is obtained by drying and granulation at the same time as drying by means of a fluidized bed, and that the average particle size of at least 85% by weight of the particles is less than 1.5 mm Antifoam granules. 2. A method for producing foam control granules for solid laundry detergents, dishwashing detergents and cleaning compositions, comprising applying an aqueous emulsion form of the silicone to an additive intermediate product of a carrier material; A method characterized in that it is granulated simultaneously with drying by a fluidized bed, and that the average particle size of at least 85% by weight of said particles is less than 1.5 mm. 3. The method according to claim 2, wherein the silicone is used together with another waxy foam control agent. 4. The method of claim 1, wherein the silicone in the form of an aqueous emulsion is
The sprayed intermediate product and optionally the waxy foam control agent are continuously sprayed onto the intermediate product, which is dried by means of a fluidized bed above a circular diffuser plate provided with through openings for drying air, and the granules are simultaneously granulated. 4. The method according to claim 2, wherein the method comprises: 5. The method according to claim 2, wherein a polysiloxane in the form of an aqueous emulsion is sprayed as the silicone. 6. The method according to claim 2, wherein the silicone in the form of an aqueous emulsion containing an inorganic or organic thickener is sprayed. 7. The method according to claim 6, wherein a mixture of sodium carboxymethyl cellulose and a nonionic cellulose ether is used as the thickener. 8. The thickener is used in an amount of 0.5 to 10% by weight, based on the aqueous silicone emulsion.
Method according to 7. 9. Spraying silicone in the form of an aqueous emulsion, the aqueous emulsion being a mixture of sodium carboxymethylcellulose and a non-ionic cellulose ether (weight ratio of cellulose / ether = 80: 20 to 40:60)
In an amount of from 0.5 to 10% by weight, based on the aqueous silicone emulsion, and starch in an amount of from 0.1 to 50% by weight, based on the aqueous silicone emulsion. 10. The method according to claim 2, wherein the silicone in the form of an aqueous emulsion is sprayed in an amount of from 5.5 to 20.0% by weight (calculated as silicone), based on the foam control granules. 11. Carrier materials include alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, alkali metal silicates, cellulose ethers,
The method according to any one of claims 2 to 10, wherein at least one substance selected from the group consisting of polycarboxylate and starch is used. 12. A substance selected from the group consisting of bisamides, fatty acids, fatty alcohols, carboxylic esters and paraffin wax as the wax-like foam controlling agent.
12. The method according to any of 2 to 11. 13. A carrier material comprising 20 to 98% by weight and 2 to 80% by weight.
13. A process according to any of claims 2 to 12, wherein an intermediate product consisting of wt% wax-like foam control agent is added. 14. Use of the antifoam granules according to claim 1 for the manufacture of solid laundry detergents, dishwashing detergents and detergent compositions.