JP2002529581A - Soluble surfactant granules - Google Patents

Abstract

  (57) [Summary] In general, surfactant granules with a high content of anionic surfactant show only limited fluidity. According to the present invention, when a faujasite-type zeolite is used during the granulation step, it is possible to produce granules that exhibit good fluidity and do not exhibit tackiness even with a high surfactant content. There was found. Based on this finding, the present invention relates to soluble surfactant granules suitable as additives in detergent compositions and / or cleaning compositions, wherein the soluble surfactant granules contain 55 to 95% by weight of anionic Granules characterized by comprising a surfactant and 5-30% by weight of faujasite-type zeolite. The present invention also provides a method for producing the granules, and a detergent and a detergent mixed with the granules.

Description

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to the use of high surfactant content granules as detergents.

[0002] According to the disclosure of EP-B-603 207, in order to produce surfactant granules for detergents having a bulk density of more than 500 g / l, a liquid component other than a surfactant is contained. The surfactant composition in the form of a liquid / paste at a pressure and temperature between 20 and 40 ° C. is dried simultaneously with the granulation. An advantage of this process of producing different types of flowable granules is that by carefully drying and eliminating dust from the granules, the discoloration of the surfactant to brown can be avoided. The composition used preferably comprises an anionic surfactant, in particular a fatty alkyl sulphate, an alkylbenzene sulphonate, a sulphofatty acid methyl ester and the like, and a nonionic surfactant. The granulation and drying processes are carried out simultaneously, by a fluidized bed, in a continuous or batch mode. The surfactant composition is introduced into the fluidized bed simultaneously or sequentially by one or more nozzles.

According to the disclosure of WO 94/07990, by neutralizing the acid of an anionic surfactant with a powdered neutralizing agent, while simultaneously granulating and optionally drying,
Manufactures anionic surfactant granules. The energy released during neutralization can be applied to drying of the granules. The surfactant granules produced in this way can contain from 20 to 70% by weight of the alkali metal carbonate excess used as neutralizing agent. Other carriers can also be used.

EP-B-683 814 discloses a method for producing surfactants having a bulk density of more than 450 g / l, according to which an acid of anionic surfactant and an alkali The aqueous solutions are exposed to the aqueous medium separately from one another and then sprayed into a granulation / drying chamber. The granulation treatment of this process can be carried out in the presence of added solids, especially alkali metal carbonates and zeolites. Zeolite A is particularly exemplified as a zeolite exhibiting a carrier action.

[0005] EP-B-707 632 discloses surfactant granules of low carbonate content exhibiting good flow properties. The granules comprise 33-55% by weight of an anionic surfactant, 30-50% by weight of zeolite and 2-25% by weight of alkali metal carbonate. When fatty alcohol sulfate is present as a single anionic surfactant, the carbonate content can be particularly reduced without losing the fluidity of the granules. As zeolite,
Although zeolite A or zeolite P is used, zeolite P is preferably used because zeolite P-containing granules have better dispersibility than zeolite A-containing granules.

(Problems to be Solved by the Invention) As described above, the prior art discloses various production methods mainly for producing high-concentration surfactant granules. Basically, however, high-concentration surfactant compounds are problematic because they exhibit only limited flowability due to their stickiness.
It is an object of the present invention to provide this solution.

DISCLOSURE OF THE INVENTION According to the present inventors, it has been found that granulation (granulation) using faujasite-type zeolite is advantageous.

[0008] According to a first aspect of the present invention, the present invention provides a soluble surfactant granule suitable as an additive for a detergent composition and / or a detergent composition, the soluble surfactant granule comprising: Comprises 55 to 95% by weight of an anionic surfactant and 5 to 3
0% by weight of faujasite-type zeolite.

[0009] The faujasite-type zeolite has a very high surfactant absorption capacity as compared to zeolite A, and also has a very high water binding capacity. Thus, the use of faujasite-type zeolites makes it possible to produce granules which exhibit free-flowing properties and exhibit no tackiness, despite the high surfactant content.

The granules according to the invention generally have a bulk density of more than 400 g / l, with granules having a bulk density of at least 500 g / l being preferred.

[0011] Particularly suitable anionic surfactants are those containing a sulfate or sulfonate group.

Sulfonate-Type Anionic Surfactants Suitable sulfonate-type anionic surfactants include C ₉ -C ₁₃ alkylbenzene sulfonates, olefin sulfonates (ie, alkene sulfonates and hydroxyalkanes). A mixture with a sulfonate), and a disulfonate. The disulfonate is, for example, double bonds with C ₁₂ -C ₁₈ mono-olefins having the inside and ends, alkaline hydrolysis it was sulfonated with sulfur trioxide gas, then the resulting sulfonated product It can be obtained by decomposition or acid hydrolysis. Other suitable sulfonate-type surfactants, with C ₁₂ -C ₁₈ alkanes, which, for example, sulfo chlorinated or sulfonated, then an alkane sulfonic acid salt obtained by hydrolysis or neutralization. Also suitable are esters of α-sulfofatty acids (ester sulfonates), such as α-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids. This methyl ester of α-sulfofatty acid is
For example, it is produced by α-sulfonating a methyl ester of a plant and / or animal-derived fatty acid having 8 to 20 carbon atoms in the fatty acid molecule, followed by neutralization to obtain a water-soluble monosalt. The α-sulfofatty acid ester is preferably an α-sulfonated ester of hydrogenated coconut oil, palm oil, palm kernel oil or tallow fatty acid, while a small amount of a sulfonated product of an unsaturated fatty acid such as oleic acid is used. , Preferably about
It may be present in an amount up to 2-3% by weight. Particularly preferred are α-sulfofatty acid alkyl esters having an alkyl chain having 4 or less carbon atoms in the ester group, such as methyl ester, ethyl ester, propyl ester and butyl ester. α
Methyl esters of sulfo fatty acids (MES) and their saponified disalts are particularly advantageous.

Sulfonated fatty acid glycerol esters Other suitable anionic surfactants are the sulfonated fatty acid glycerol esters, ie, monoesters, diesters and triesters, and mixtures thereof. Sulfonated fatty acid glycerol esters consist of monoglycerol and fatty acids.
Esterification reaction with 1-3 mol or triglycerol and glycerol
It can be obtained by transesterification with 0.3 to 2 mol.

Alkyl (alkenyl) sulphates Suitable alkyl (alkenyl) sulphates are the alkali metal salts, especially the sodium salts, of sulfuric acid semiesters of fatty alcohols. As the fatty alcohols, C ₁₂ -C ₁₈ fatty alcohols, for example, coconut oil fatty alcohols, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol and the like, also C ₁₀ -C ₂₀ oxo alcohols, and the same chain length Secondary alcohols are exemplified. Other suitable alkyl (alkenyl) sulphates are those having the above-mentioned chain length and containing synthetic straight-chain alkyl chains of petrochemical systems and exhibiting similar disintegration behavior to the corresponding compounds of fat and oil chemistry raw material systems. It is. From the viewpoint of the washing processing performance,
C ₁₂ -C ₁₆ alkyl sulfates, C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are especially preferred. Other suitable anionic surfactants are 2,3-alkyl sulphates, which can be prepared, for example, by the methods described in US 3,234,258 or US 5,075,041 and are commercially available as DAN® (Shell Oil Company) Have been.

Anionic Surfactants In addition to the ethylene oxide adduct , other anionic surfactants can be used, for example, linear / branched, ethoxylated with 1 to 6 mol of ethylene oxide (EO). Sulfuric acid monoesters of C ₇ -C ₂₁ alcohols, for example, sulfuric acid monoesters of 2-methyl branched C ₉ -C ₁₁ alcohols (EO average 3.5 mol) or sulfuric acid monoesters of C ₁₂ -C ₁₈ fatty alcohols (EO 1- 4 mol) are also suitable. Fatty acid derivatives of amino acids Other suitable anionic surfactants include fatty acid derivatives of amino acids, such as fatty acid derivatives of N-methyltaurine (tauride) and / or fatty acid derivatives of N-methylglycine (sarcoside). Preference is given to sarcosides or sarcosinates, especially sarcosinates of higher fatty acids, which are optionally mono- or polyunsaturated, such as oleyl sarcosinate.

Anionic Surfactant in Salt Form The anionic surfactant may be present in the form of a sodium, potassium or ammonium salt and may be an organic base such as mono-, di- or tri-ethanol. It can be present as a soluble salt of the amine. The anionic surfactant may suitably be present in the form of a sodium or potassium salt, in particular in the form of a sodium salt.

Preferred Anionic Surfactants According to the Invention According to the invention, preferred granules contain an anionic surfactant of the sulfonate type. In order to improve the solubility behavior, the granules according to the invention advantageously contain, in addition to the sulphonate-type surfactant, the sulphate-type anionic surfactant. According to a preferred embodiment of the present invention, the granules of the present invention, in addition to the sulfonate (sulfonate) type anionic surfactants, C ₁₂ -C ₁₈ alkyl sulfate (sulfate), in particular, C ₁₂ include -C ₁₄ alkyl sulfates, the sulfonate (sulfonate) surfactant weight ratio of the sulfate ester (sulfate) surfactant is 1: 1 to 20: 1, in particular, 2: 1 10: 1.

Nonionic Surfactant The granules of the present invention can contain a nonionic surfactant in addition to the anionic surfactant. Suitable nonionic surfactants are alkoxylated, preferably ethoxylated alcohols, especially primary alcohols, and alkyl glycosides of the formula RO (G) _x . The former preferably comprises an alcohol having 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mol of alcohol. Relates latter, R represents a primary, linear or methyl branched (in particular, 2-methyl-branched) C ₈ -C _22, and preferably a C ₁₂ -C ₁₈ aliphatic group. G is a glucose unit having 5 or 6 carbon atoms (preferably a glucose unit). The degree of oligomerization x indicates the distribution of monoglycosides and oligoglycosides, is any desired number, is a number determined by analysis, may be a fraction, preferably a number from 1 to 10, More preferably 1.2 to
It is a numerical value of 1.4.

In addition to water , the granules according to the invention preferably contain only small amounts of water as sole medium. This is because the flowability of high concentration surfactant granules clearly decreases with increasing water content. According to one preferred embodiment of the invention, the granules comprise less than 7% by weight of water, especially when the surfactant content is greater than 70% by weight.
The granules suitably contain less than 4.5% by weight of water.

Carriers From this point of view, particularly suitable carriers are compounds which are capable of absorbing moisture and which can prevent anionic surfactants from exhibiting tackiness. Use of this type of carrier can improve the flowability and solubility behavior of the granules, and can improve the storage stability of the granules.

Suitable carriers for this purpose are faujasite-type zeolites and, for example, calcined soda and overdried amorphous silicates.

The faujasite-type zeolite faujasite-type zeolite is represented by the formula: _{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O. Wherein M is an n-valent cation, x is a numerical value of 2 or more, and y is 0 to 20.
Is the numerical value of. The structure of zeolites is formed by the linkage of AlO ₄ tetrahedra to SiO ₄ tetrahedra, the skeleton of which is occupied by cations and water molecules. The cations in such a structure are relatively mobile and can be replaced by other cations in various proportions. Crystallized water (zeolite water) can be released continuously and reversibly, depending on the type of zeolite, while certain zeolite types are accompanied by structural changes due to the release and absorption of water.

In the structural unit, the “primary structural unit (AlO ₄ tetrahedron and SiO ₄ tetrahedron)” is
Form "secondary structural units" which are considered to be in mono- or polycyclic forms. For example, in various zeolites, single-, six- and eight-membered rings (referred to as S4R, S6R and S8R) are formed, while other types of zeolites form a dual four-membered ring. Rings are linked by double ring prisms of double and six-membered rings (the most common type: D4R as square prism and D6R as hexagonal prism). "Secondary structural units" are linked to various polyhedra represented by Greek letters. The most common of which is a polyhedron constructed by six squares and eight equal area hexahedra,
It is called "β". Various zeolites can be produced from such structural units. Currently, 34 natural zeolite minerals and about 100 synthetic zeolites are known.

Faujasite minerals, together with zeolites X and Y, belong to the faujasite type of zeolite structural group 4 characterized by a double 6-membered ring (D6R) structural unit [Donald W. Bre
ck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, p. 92]. In addition to faujasite-type zeolites, chabazite mineral (olivine), gmelinite mineral (gomerite), synthetic zeolite R (chabazite type), synthetic zeolite S (gmelinite type) and synthetic zeolite L, and synthetic zeolite ZK-5 Belongs to the zeolite structure group 4. Of these synthetic zeolites, the last two do not have any mineral analogs.

Faujasite-type zeolites are composed of β-cages tetrahedrally linked by D6R structural units, and the β-cages have an arrangement similar to the carbon element in diamond. The three-dimensional framework of faujasite-type zeolite used in the present invention has pores of 2.2 to 7.4 ° in size. In addition, the element vesicle has eight cavities with a diameter of about 13 ° and is represented by the formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .264H ₂ O. The framework of zeolite X has a porosity of about 50% (based on dehydrated crystals) and has the largest cavity of all known zeolites (zeolite Y = about 48% porosity, faujasite-type zeolite = about 47 % Porosity). All of the above data can be found in the following document: Donald W. Breck: "Zeolite Molecular Sieves", Jhon Wieley & Sons, New York, London, Sydney, Toronto, 1974, 145, 176, 177.

The term “faujasite-type zeolite” as used herein refers to all three zeolites that constitute the faujasite subgroup of zeolite structure group 4 [Don
ald W. Breck: "Zeolite Molecular Sieves", Jhon Wieley & Sons, New York, London, Sydney, Toronto, 1974, p. 92]. Thus, according to the present invention, in addition to zeolite X, zeolite Y and faujasite-type zeolites and mixtures of these compounds can also be used, but zeolite X alone is preferred.

According to a mixture or co-crystallizate present invention with other zeolites, mixtures or co-crystallizate of faujasite-type zeolite with other zeolites, inevitably, there is one not belonging to the zeolite structure group 4 But,
It can be used in the present invention. According to the present invention, the advantage of the present invention becomes particularly clear when at least 50% of the zeolite present in the surfactant-containing granules is composed of faujasite-type zeolite.

X-type zeolite A commercially available X-type zeolite is represented by the following formula, for example. Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · xH ₂ OK ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · xH ₂ O Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ XH ₂ O Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] xH ₂ O In the above formula, x is a numerical value from 0 to 276, and the pore size is 8.0 to 8.4Å.

A eutectic of zeolite X and zeolite A, for example, a eutectic of zeolite X and zeolite A (about 80% by weight of zeolite X)
Is commercially available [CONDEA Augusta SpA, VEGOBOND AX (registered trademark)], represented by the following formula, and can be advantageously used in the method of the present invention. nNa ₂ O ・ (1-n) K ₂ O ・ Al ₂ O ₃・ (2-2.5) SiO ₂・ (3.5-5.5) H ₂ O

Y-type zeolite Y-type zeolite is also commercially available, and is represented by the following formula, for example. Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] · xH ₂ O, K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] · xH ₂ O In the above formula, x is a number from 0 to 276. The pore size is about 8.0 mm.

The microcrystals, in addition to the bound water-containing synthetic zeolite faujasite-type zeolite, microcrystalline, bound water-containing synthetic zeolites, for example, a mixture of zeolite A, zeolite P and zeolite A and zeolite P. Zeolite MAP® (Crosfield) is an example of a commercially available zeolite P.

Particle size: zeolite The zeolite used in the method of the present invention has a particle size of 0.1 to 100 μm, preferably 0.5 to 100 μm.
It is 50 μm, especially 1 to 30 μm (measured by standard methods of particle size measurement).

Content: Zeolite In the granules of the present invention, the content of faujasite type zeolite is 5 to 30% by weight. For producing particularly high concentrations of surfactant granules, particularly preferably, the granules according to the invention comprise exclusively from 5 to 20% by weight of faujasite-type zeolites. If other carrier materials are used in addition to the faujasite-type zeolite, the faujasite-type zeolite is preferably present in an amount of less than 15% by weight.

Morphology: Faujasite-type zeolite In order to increase the storage stability of the granules according to the invention, faujasite-type zeolites are used in an overdried form, the water content of which can be removed at 800 ° C.
Less than the equilibrium water content of the zeolite used.

Carbonate According to one preferred embodiment of the invention, the granules according to the invention are, as additional carriers, alkali metal carbonates, preferably sodium carbonate (or soda), in particular calcined sodium carbonate. And the weight ratio of alkali metal carbonate: faujasite type zeolite is 5
: 1 to 1: 5, preferably 2: 1 to 1: 3.

As mentioned above, other zeolites in the over-dried form or amorphous alkali metal silicates (so-called water glass), crystalline layered silicates, sodium sulfate and trisodium citrate may also be used as additional carrier components. Can be present.

According to another aspect of the present invention, the present invention is directed to a method of making soluble surfactant granules suitable as an additive in a detergent composition and / or a detergent composition, comprising at least one surfactant Granulating and drying the water-containing paste of activator or surfactant precursor, preferably simultaneously with the inorganic carrier component, wherein each of the liquid components is mixed and then introduced into a granulation chamber, or The present invention provides a method characterized by spraying independently and separately into a chamber and using faujasite-type zeolite as an inorganic carrier component.

In the method of the present invention, the above-mentioned surfactant can be used as the surfactant, and the anionic surfactant can be preferably used in the form of its acid precursor.

According to a preferred embodiment of the present invention, when the surfactant is used in the form of an aqueous composition of an anionic surfactant acid, an alkaline aqueous solution is used for the neutralization treatment of the spray. This spray neutralization treatment can be performed simultaneously with the granulation step.

Granulation Step The granulation step can be carried out with a suitable granulator. However, the granulation step can suitably be carried out batchwise or in a continuous fluidized bed. According to a preferred embodiment of the present invention, the method can be continuously performed by a fluidized bed. In this case, the liquid composition can be introduced into the fluidized bed by a mono- or multi-component nozzle or several nozzles.

Carrier Material The carrier material used in the present invention is a carrier as described above. With regard to the process of the invention, it is particularly preferred that the zeolite is used in an overdried form, the water content of the zeolite that can be removed at 800 ° C. is less than the equilibrium water content of the zeolite used, Is overdried just before granulation. As used herein, the term "excessive drying" refers to a treatment that reduces the water content that can be removed at 800 ° C. Generally, overdrying is performed by heat treating the zeolite prior to its introduction into the granulation chamber, but according to another preferred embodiment of the invention, the solid zeolite is first placed in the granulation chamber. It is introduced and then heat-treated there by airflow, after which the other components are sprayed into the chamber.

Incorporation of Solid and Liquid Components The carrier component and other solid components present in the granules according to the invention can be introduced in a gas stream by means of a blowing pipe or in the form of a liquid or suspension mixture with a liquid. Can be introduced. In the former case, the carrier component and other solid components can be added before or during the spraying of the liquid component. The liquid components can be mixed before spraying or mixed in a nozzle. The nozzles can be arranged in any manner, spray angle and spray direction as long as a substantially uniform distribution of the liquid components in the fluidized bed can be achieved.

Fluidized bed granulator Suitable fluidized bed granulators comprise a base plate with dimensions of at least 0.4 m. The base plate of the fluidized bed is suitably 0.4-5 m in diameter, e.g. 1.
It has a diameter of 2 to 2.5 m. However, fluidized beds with a base plate having a diameter of more than 5 m are also suitable. Base plate with through holes or so-called Conidur
A plate (producer: Hein & Lehmann, Federal Republic of Germany) can be suitably used as the base plate. The process of the present invention can be carried out preferably at a fluidizing gas flow velocity of 1 to 8 m / sec, preferably 1.5 to 5.5 m / sec.

Classification Step The granules are advantageously removed from the fluidized bed through a classification step. The classification process is
For example, with a sieve or countercurrent dry air stream (classifying air) to remove only granules of a size greater than a predetermined size from the fluidized bed while leaving smaller size particles in the fluidized bed. To do. According to one preferred embodiment of the present invention, the air flow comprises:
Composed of heated air or unheated classification air and heated bottom air. The temperature of the bottom air is preferably between 80 and 400C, preferably between 90 and 350C. The air stream is cooled via heat loss and heat of evaporation of the solvent component. According to one particularly preferred embodiment of the invention, the air flow about 5 cm above the base plate has a temperature of about 60-120C, preferably 70-100C. The temperature of the outlet air stream is 60-120 ° C., preferably 100
It is below ° C.

As disclosed in EP-B-0 603 207, if the granules are removed from the fluidized bed by a stream of air for classification, the granules obtained by this classification process do not contain dust, and the particle size is
Exceeds 0.2 mm. According to the present invention, the preferred granules, d ₅₀ value of 0.4 to 2.0 mm.
According to a preferred embodiment of the present invention, particles having a particle size of more than 2.0 mm are returned. After classification, such a coarse particle fraction can be added as a solid component to the fluidized bed or redissolved and sprayed into the fluidized bed.

Powdering Agent According to the granulation method of the present invention, a so-called powdering agent can be continuously introduced into a fluidized bed to maintain the fluidized bed fluidizing method. Zeolites are preferably used as powdering agents, and the zeolites used according to the invention as carriers are particularly suitable powdering agents. These powdered materials can prevent the wet granules from becoming sticky during the granulation process and promote fluidization and drying, thereby forming the desired product. The particle size of the powdering agent is 100 μm and the resulting granules can contain from 1 to 4% by weight of the powdered material. This variant of the addition of the powdering agent is advantageous for the production of the granules according to the invention, but is not an essential step.

According to another aspect of the present invention, there is provided a detergent composition and / or detergent composition comprising at least one soluble surfactant granule and other components, the composition comprising: The surfactant granules provide a composition characterized by being granules selected from the group consisting of the surfactant granules of the present invention and the surfactant granules obtained by the method of the present invention.

The detergents according to the invention, which can be present as solids or other compacts in granular (granular), powder or tablet form, are, in addition to the substances mentioned, in principle known components which are common to detergents Can be included. According to the invention, suitable detergents are granular detergents, in particular those obtained by mixing granules of various detergent components.

Surfactants In the detergent of the present invention, the most important components include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and / or zwitterionic surfactants. Is exemplified.

Anionic surfactants Suitable anionic surfactants are, in particular, those surfactants which are preferably used according to the invention in the form of granules. Other suitable anionic surfactants are, in particular, soaps, the dose of which is between 0.2 and 5% by weight. Suitable soaps are, in particular, those of saturated fatty acids, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and especially natural fatty acids (eg coconut oil, palm kernel oil) Or a tallow fatty acid).

The anionic surfactant can be present in the form of a sodium, potassium or ammonium salt and can also be present as a soluble salt of an organic base, for example mono, di or triethanolamine. The anionic surfactant is suitably present in the form of a sodium or potassium salt, especially the sodium salt. In the detergent of the present invention, the content of the anionic surfactant is preferably 1 to 35% by weight, more preferably 5 to 35% by weight.
~ 30% by weight.

Nonionic surfactants Suitable nonionic surfactants are also the above-mentioned surfactants. Suitable nonionic surfactants are alkoxylated (preferably ethoxylated) alcohols, especially primary alcohols. It preferably consists of an alcohol having 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, the alcohol residues being straight-chain or preferably 2-methyl-branched. It may be present or may have a mixture of linear and methyl branch groups as in normal oxo alcohol residues. However, alcohol ethoxylates having linear groups of C _12-18 alcohols of natural origin (for example coconut fatty alcohol, palm oil fatty alcohol, tallow fatty alcohol or oleyl alcohol) and an average of 2 to 8 EO per mol of alcohol Is particularly preferred. Suitable ethoxylated alcohols, e.g., C _12-14 alcohols + 3EO or 4 EO, C _9-11 alcohol + 7 EO, C _13-15 alcohols + 3EO, 5 EO, 7 EO or 8EO, C _12-18 alcohol + 3EO, 5 EO or 7 EO, and mixtures thereof (e.g., a C _12-14 alcohol + 3EO, a mixture of C _12-18 alcohol + 7 EO) are exemplified. The ethoxylation degree is a statistical average, which is
For a particular product, it may be an integer or a fraction. Suitable alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to such non-ionic surfactants, fatty alcohols having an EO greater than 12 as described above may also be used. Examples are (tallow) fatty alcohol + 14EO, 16EO, 20EO, 25
EO, 30EO or 40EO.

Examples of the alkyl glycoside nonionic surfactant include an alkyl glycoside represented by the formula: RO (G) _x . Wherein R is a C ₈ -C ₂₂ , preferably C ₁₂ -C ₁₈ aliphatic group of primary, straight-chain or methyl-branched (particularly 2-methyl-branched). G is carbon number 5 or 6
Is a glucose unit (preferably a glucose unit). The degree of oligomerization x indicates the distribution of monoglycosides and oligoglycosides and may be a fraction as an analytical measurement, a value between 1 and 10, preferably between 1.2 and 1.4.

Polyhydroxy fatty acid amides Another suitable surfactant is a polyhydroxy fatty acid amide of the following formula (I):

Embedded image In the above formula, R ¹ CO is an aliphatic acyl group having 6 to 22 carbon atoms, R ² is hydrogen, and 1 to 4 carbon atoms.
Is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amide can suitably be obtained from a reducing sugar having 5 or 6 carbon atoms, especially glucose.

Polyhydroxy fatty acid amides A group of polyhydroxy fatty acid amides is exemplified by compounds represented by the following formula (II).

Embedded image In the above formula, R ³ is a C ₇ -C ₁₂ linear or branched alkyl or alkenyl group, R ⁴ is a C ₂ -C ₈ linear, branched or cyclic alkyl group or An arylene group, R ⁵ is a C ₁ -C ₈ linear, branched or cyclic alkyl or aryl or oxyalkyl group, preferably a C ₁ -C ₄ alkyl or phenyl group, and [ Z] is a linear polyhydroxyalkyl group in which the alkyl chain is substituted by at least two hydroxyl groups or an alkoxylated derivative thereof, preferably an ethoxylated or propoxylated derivative. As before, [Z] is preferably obtained by reductive amination of a saccharide such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. Further, an N-alkoxy-substituted or N-aryloxy-substituted compound can be reacted with a fatty acid methyl ester in the presence of an alkoxide as a catalyst to convert the compound into a desired polyhydroxyfatty acid amide (for example, WO95 / 07331).

Alkoxylated fatty acid alkyl esters Another group of suitable nonionic surfactants are those which can be used alone or other nonionic surfactants, especially alkoxylated fatty alcohols and / or alkyl glycosides. A surfactant that can be used in combination with
Alkoxylated (preferably ethoxylated or ethoxylated and propoxylated) fatty acid alkyl esters. The alkoxylated fatty acid alkyl ester is preferably an ester having 1 to 4 carbon atoms in the alkyl chain, in particular, a fatty acid methyl ester (see the production method described in JP58 / 217598 or WO90 / 13533).

Nonionic surfactants of the amine oxide type / fatty acid alkanolamide type Nonionic surfactants of the amine oxide type (for example, N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide) and nonionic surfactants of the fatty acid alkanolamide type are also preferably used. The dose of these nonionic surfactants is preferably smaller than the dose of ethoxylated fatty alcohol, in particular smaller than half the dose of ethoxylated fatty alcohol.

Gemini surfactants Other suitable surfactants are the so-called Gemini surfactants. Gemini surfactants are generally understood to be compounds having two hydrophilic and two hydrophobic groups per molecule. These groups are generally separated from one another by so-called spacers. The spacer is generally a carbon chain, which must be long enough so that the hydrophilic and hydrophobic groups have sufficient spacing to be able to act independently of each other. Gemini surfactants are generally characterized by significantly lower critical micelle concentrations and the ability to significantly lower the surface tension of water.
However, in some cases, gemini surfactants are understood to be not only dimeric surfactants, but also trimer surfactants. Suitable gemini surfactants include sulfated hydroxy mixed ethers (DE-A-432
1022) and dimer alcohol bissulfate, trimer alcohol tris sulfate and dimer / trimer alcohol ether sulfate (DE-A-1950306)
1) is exemplified. Mixed end-capped dimer and trimer ether (DE-A-1951
3291) are particularly characterized by their bifunctional and polyfunctional nature. That is, this end group cap surfactant exhibits good wetting properties, and exhibits low foaming properties.
Particularly suitable for use in washing or washing processes with a washing machine. However, gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides (WO-A-95 / 19953, WO-A-95 / 19954 and WO-A-95 / 19955) can also be used.

Builders The detergents of the present invention are of the builder type, ie at least one organic builder and / or
Or an inorganic builder may be included. Organic builders Suitable organic builders, provided that they are ecologically safe for use, for example,
Useful polycarboxylic acids (e.g. in the form of the sodium salt), examples of which are citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and the like. 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.

As the salt builder of the polymer polycarboxylic acid, besides the polycarboxylic acid in the monomer form, a salt of the polymer polycarboxylic acid can also be used. Suitable polymeric polycarboxylic acid salts include, for example, the sodium salt of polyacrylic acid or polymethacrylic acid, for example, having a relative molecular weight of 80.
It is a salt of 0 to 150,000 (acid standard, measured using polystyrene as a standard). 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 suitable acrylic / maleic acid copolymers have been found to be 50-90% by weight acrylic acid and 50-10% by weight maleic acid copolymers. Its relative molecular weight is generally from 5,000 to 200,000, preferably from 10,000 to 120,000, more preferably from 50,000 to 100,000, based on the free acid (measured using polystyrene as a standard).

Dosage: Salts of polymeric polycarboxylic acids (co) The salts of polymeric polycarboxylic acids can be used in detergents in the usual doses, preferably in doses of 0.1 to 10% by weight.

Biodegradable polymers Particularly preferably, biodegradable polymers consisting of two or more different monomer units are used. For example, a biodegradable polymer containing a monomer of acrylic acid and maleic acid and vinyl alcohol or a derivative thereof (DE-A1 43 00 772),
Alternatively, a biodegradable polymer (DE-A1 42 21 381) containing, as monomers, a salt of acrylic acid and 2-alkylallylsulfonic acid and a sugar derivative is exemplified.

Other suitable copolymers Other suitable copolymers are the copolymers described in DE-A-43 03 320 and DE-A-44 17 734, which are preferably acrolein and acrylic acid / salts thereof, Or it contains acrolein and vinyl acetate as monomers.

[0064] acid acid may be used in native form. Acids, in addition to their builder action, also generally exhibit properties as acidifying components and can be used to lower or moderate the pH of laundry detergent or cleaning compositions.

Dextrins Another useful organic builder is 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. Maltodextrins with DE 3-20 and dry glucose syrups with DE 20-37 and relatively high molecular weight yellow and white dextrins with an average molecular weight of 2,000-30,000 can also be used. Suitable dextrins are the substances described in GB-A1-94 19091. 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
-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042, EP-A-0 542 496, WO 92 /
18542, WO 93/08251, WO 94/28030, WO 95/07303, WO 95/12619, WO 95/2060
8. Products oxidized at the 6-position carbon of the sugar ring are particularly preferred.

Cobuilders Other suitable cobuilders are oxydisuccinates and derivatives thereof, 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. The dose of the zeolite and / or silicate containing composition is between 3 and 15% by weight.

Organic Cobuilders Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids and their salts, which may be present in lactone form, having at least 4 carbon atoms, at least one hydroxy group and at most one Contains two acidic groups. These cobuilders are described, for example, in WO 95/20029.

Builders: Oxidation Products of Carboxyl-Containing Polyglucosan Other suitable builders are the oxidation products of carboxyl-containing polyglucosan and / or their water-soluble salts (for example WO-A-93 / 08251 or WO -A-93 / 16110
). Oxidized oligosaccharides (DE-A-196 00 018) are also suitable.

Builders: Amino Carboxylic Acid Polymers Other suitable builders are amino carboxylic acid polymers and their salts or precursors thereof. Polyaspartic acid and its salts or their derivatives (DE-A
-195 40 086) is particularly suitable because it exhibits a bleaching stabilizing effect in addition to the cobuilder properties.

Builders: Polyacetals Another preferred builder is polyacetal, which comprises a dialdehyde,
It can be obtained by reacting with a polyol carboxylic acid (5-7 carbon atoms and at least three hydroxy groups) (EP-A1-0 280 223). 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.

Inorganic builders Suitable inorganic builders are microcrystals and synthetic zeolite containing bound water. In the present invention, faujasite-type zeolite is an essential component. Other zeolites that can be suitably used as builders are zeolite A and zeolite P. However, mixtures of zeolites A, X, Y and / or P are preferred. Zeolite
MAP® (Crosfield) is an example of a commercially available zeolite P. However, zeolites X and mixtures of zeolites A, X and / or P are also suitable. Eutectic sodium aluminosilicate of zeolite X and zeolite A /
Potassium is also suitable for the present invention, for example a commercial product (VEGOBOND AX®, CONDEA Augusta S. p.A.). The zeolites can be used in the form of a spray-dried powder or in the form of a wet stabilized suspension which is moistened by production. If the zeolite is used in the form of a suspension, the suspension may further contain small amounts of non-ionic surfactants or stabilizers, and as non-ionic surfactants, based on the weight of the zeolite, 1-3% by weight of ethoxylated _C12-18 fatty alcohols (containing 2-5 mol EO), _C12-14 fatty alcohols (containing 4-5 mol EO) or ethoxylated isotridecanol. Suitable zeolites have an average particle size of less than 10 μm (Coult
er Counter Method) and preferably 10 to 2
It contains 4% by weight, more preferably 15-22% by weight of bound water. According to the invention, at least some of the inorganic builders are faujasite-type zeolites, which can be introduced into the detergent via the inventive granules or the granules obtained by the inventive process. .

Inorganic builders: Layered silicates Some or all of the substitutes for zeolites are natural and synthetic layered silicates. Layered silicates are disclosed, for example, in the following document: DE-B-23 34 899, EP
-A- 0 026 529 and DE-A-35 26 405. The layered silicate is not limited to a specific compositional formula. However, smectites, especially bentonite, are preferred. Suitable substitute materials of the zeolite and phosphate is a crystalline layered sodium silicate, which is represented by the formula: _{NaMSi x O 2x + 1 yH 2} O. Wherein M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and a preferred value for x is 2, 3 or 4. Such crystalline layered silicates are described, for example, in EP-A-0 164
514. Preferred crystalline sheet silicates of the above formula are those wherein M is sodium and x
Is a silicate having a numerical value of 2 or 3. Both β- and δ-sodium silicates of the formula: Na ₂ Si ₂ O ₅ yH ₂ O are particularly preferred.

Inorganic builders: amorphous sodium silicate. Other useful builders include a coefficient (ratio of Na ₂ O: SiO ₂ ) of about 1: 2 to about 1: 3.3, preferably about 1: 2 to 1: 2.8. And more preferably amorphous sodium silicate having a ratio of about 1: 2 to 1: 2.6, which, due to delayed dissolution, exhibits multiple wash cycle characteristics. With prior art amorphous sodium silicate, delayed dissolution can be obtained in various ways, such as by surface treatment, compounding treatment, compression or overdrying. The term "amorphous" as used herein refers to X-ray 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 is described as meaning that the crystallite area of the product has a size of 10 to several hundreds nm (up to 50 nm), the size of which is particularly preferably up to 20 nm. . Such so-called X-ray amorphous silicates exhibiting delayed dissolution properties than ordinary water glass are described in DE-A-44 00 024. Compressed amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred. Overdried silicates are particularly suitable as carriers for the granules according to the invention and as carriers for the method according to the invention.

Inorganic builders: phosphates Known phosphates can of course be used as builder substances, provided they are ecologically sound. Preferred 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, especially with small amounts (eg, up to 10% by weight based on the final detergent composition), along with other builders, can provide a synergistic improvement in multiple wash cycle performance. Turned out to be.

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 perbenzoate, peroxyphthalic acid A salt, diperazelinic acid, phthalimino peracid or diperdocanedioic acid. The bleach content in the detergent is preferably from 0 to 30% by weight, more preferably from 5 to 25% by weight, and perborate monohydrate or percarbonate is advantageously used.

[0076] When performing the washing with bleach activators 60 ° C. or lower temperature, to obtain a high bleaching effect, it is possible to mix the bleach activator in the composition. Examples of bleach activators are N-acyl and O-acyl compounds which form an organic peracid with hydrogen peroxide, preferably N, N'-tetraacylated diamine, acylated glycoluril, especially tetraacetylglycoluril, N-acylhydatoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates, carboxylic esters such as p-
(Alkanoyloxy) benzenesulfonates, especially isononanoyloxybenzenesulfonate, p- (alkenoyloxy) benzenesulfonate, etc., caprolactam derivatives, carboxylic anhydrides, especially phthalic anhydride, esters of polyols, such as glucose pentaacetate, etc. . Other known bleach activators include acetylated mixtures of sorbitol and mannitol, for example the substances described in EP-A-0 525 239 and acetylated pentaerythritol. In the bleach-containing detergent, the water content of the bleach activator is a usual amount, preferably 1 to 10% by weight, more preferably 3% by weight.
~ 8% by weight. Particularly suitable bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) And acetylated sorbitol-mannitol mixture (SORMAN
). According to the invention, the bleaching activator can be coated with a film-forming substance or granulated or extruded / pelletized in a customary manner, and then, if desired, compounded and granulated according to the invention. The size can be increased by the use of auxiliaries, in particular methylcellulose and / or carboxymethylcellulose, and, if desired, additional additives such as dyes. The granules according to the invention preferably contain a bleach activator in an amount of more than 70% by weight, preferably in an amount of 90-99% by weight. Bleaching activators that form peracetic acid under washing conditions can also be suitably used.

Bleaching Catalyst In addition to or instead of the conventional bleaching activators described above, sulfonymines (
EP 0 446 982, EP 0 453 003) and / or bleach-promoting transition metal salts or complexes can be used as so-called bleach catalysts. Examples of suitable transition metal compounds are, in particular, the following substances: manganese-, iron-, cobalt-, ruthenium- or molybdenum-selenium complexes (DE 195 29 905 A1) and their N-
Analogous compounds (DE 196 20 267 A1), manganese-, iron-, cobalt-, ruthenium- or molybdenum-carbonyl complexes (DE 195 36 082 A1), manganese, iron, cobalt, including nitrogen-containing tripodal ligands , Ruthenium, molybdenum, titanium, vanadium and copper complexes (DE 196 05 688 A1), cobalt-, iron-, copper- and ruthenium-amine complexes (DE 196 20 411 A1), manganese, copper and cobalt complexes (DE 44
16 438 A1), cobalt complex according to EP 0 272 030 A1, manganese complex according to EP 0 693 550 A1, manganese, iron, cobalt and copper complex according to EP 0 392 592, EP 0 443 651 or EP 0 458 397 A1, EP 0 458 398 A1, EP 0 549 2
A manganese complex according to 71 A1, EP 0 549 272 A1, EP 0 544 490 A1, and EP 0 544 519 A1. Combinations of bleach activators and transition metal bleach catalysts are described, for example, in DE 196 13 10
3 A1 and WO 95/27775. Bleaching-enhanced transition metal complexes, especially
Using a bleach-enhancing transition metal complex, such as having manganese, iron, cobalt, copper, molybdenum, vanadium, titanium and / or rubidium as the central atom, the dosage of which is preferably based on the total amount of the composition, Amount up to 1% by weight, more preferably 0
.0025-0.25% by weight, most preferably 0.01-0.1% by weight.

Enzymes Enzymes which may optionally be used in the detergents of the present invention are proteolytic enzymes (proteases), starch hydrolyzing enzymes (amylases), pullulanases, cellulases, cutinases and / or lipolytic enzymes (lipases). Suitable proteolytic enzymes are, for example, BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Puraf
ect® OxP, Esperase® and / or Savinase®. Suitable starch hydrolases are, for example, Termamyl®, Am
ylase-LT (registered trademark), Maxamyl (registered trademark), Duramyl (registered trademark), Purafect
(Registered trademark) OxAm. Suitable cellulases are, for example, Celluzyme®, Carezyme®, KAC®. WO 96/34108 and WO 96 /
The cellulase and lipolytic enzyme described in 34092 are, for example, Lipolase (registered trademark)
, Lipomax®, Lumafast® and / or Lipozym®. Enzymes can also protect them from premature inactivation by absorption into carrier substances and / or encapsulation with membrane materials (WO 92/11
347 or WO 94/23005). The enzyme can be present in the detergent according to the invention preferably in an amount of up to 10% by weight, more preferably in an amount of 0.05 to 5% by weight. Enzymes stabilized against oxidative degradation are particularly preferred (WO 94/02597, WO 94/02618, WO 94/1831
4, WO 94/23053 or WO 95/07350).

Stabilizers Suitable stabilizers for compounds and enzymes sensitive to heavy metal ions are polyphosphonates, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid. (DETPMP) or ethylenediaminetetramethylenephosphonic acid.

Grease-Removing Component The detergent of the present invention may further contain a component for promoting removal of grease from textiles by washing. This accelerating effect is evident, in particular, when textiles which have already been laundered repeatedly with the detergent according to the invention, which contain grease-soluble components, become soiled. Suitable oil dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose (
Each containing from 15 to 30% by weight of methoxy groups and from 1 to 15% by weight of hydroxypropyl groups, based on the amount of nonionic cellulose ether), and known phthalic and / or terephthalic acid polymers and derivatives thereof, In particular, polymers of ethylene terephthalate and / or polyethylene glycol terephthalate and their anionic and / or nonionic modified derivatives are exemplified. Of these, the sulphonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

[0081] Seiawazai When using detergents of the present invention in a washing machine, a conventional suds control agent advantageously be added to the detergent. Suitable Seiawazai are, for example, natural and synthetic soaps containing C _{18 to 24} fatty acids with a high content. Suitable non-surfactant-type foam control agents are, for example, organopolysiloxanes and also mixtures of organopolysiloxanes with optionally silanized silica or bisstearylethylenediamine. Mixtures of different antifoams, for example mixtures of silicone, paraffin and wax, can also be used to advantage. The foam control agent, especially a silicone and / or paraffin-containing foam control agent, is suitably fixed to a particulate water-soluble or water-dispersible carrier. Mixtures of paraffin and bisstearylethylenediamine are particularly preferred.

[0082] function of redeposition inhibitors redeposition agents in laundry solution, the dirt separated from the suspending fibers, and held at this separated state, and to prevent the reabsorption of contamination with wash. Suitable anti-redeposition agents are water-soluble and are generally organic colloids. For example, water-soluble salts of polymer carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, and acid sulfates of cellulose or starch are exemplified. For this purpose, water-soluble polyamides containing acidic groups are preferred. Other water-soluble and other starch products can also be used, examples of which include degraded starch, aldehyde starch and the like. Polyvinylpyrrolidone is also suitable. However, cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone,
It is preferably used in an amount of 0.1 to 5% by weight, based on the weight of the detergent.

Fluorescent Whitening Agent The tablet of the present invention may contain a derivative of diaminostilbene disulfonic acid or an alkali metal salt thereof as a fluorescent whitening agent. Suitable optical brighteners are, for example, salts of 4,4′-bis- (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2′-disulfonic acid, Or a compound having a similar structure and having a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group instead of the morpholino group. Substituted diphenylstyryl type optical brighteners can also be used, such as 4,4'-bis- (2-sulfostyryl) diphenyl, 4,4'-bis- (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4
An alkali metal salt of '-(2-sulfostyryl) diphenyl is exemplified. Mixtures of the above whitening agents can also be used.

Other Detergent Ingredients The detergent of the present invention may contain, in addition to the components described above, known additives generally used in laundry detergents, dishwashing detergents and cleaners. Small amounts of filler neutral salts, dyes, fragrances, brighteners, pearlescent agents, and the like.

Bulk Density The bulk density of the granules according to the invention is at least 600 g / l, preferably between 650 and 1,100 g / l. However, detergents having a lower bulk density can also be easily produced. This is particularly suitable when the detergent is composed of individual granule components per building block.

EXAMPLES Using a fluid bed dryer, the granules of the present invention, Examples E1 to E3 and E6 to E9, were produced. For the manufacture, an aqueous composition of a particular anionic surfactant acid and a neutralizing agent,
Together, they were introduced into the fluidized-bed chamber by means of a two-component nozzle and simultaneously sprayed with the zeolite. By this spray neutralization method, a compound having a composition shown in Table 2 was produced using the process parameters shown in Table 1.

For the production of Examples E4, E5 and E10 of the present invention and Comparative Examples C1 and C2,
Surfactant aqueous paste, together with the carrier component, is directly introduced into the fluidized bed dryer,
Granulated (granulated) and dried.

[0088]

[Table 1]: Process parameters

The product obtained by the continuous process has a bulk density and a water content that can be controlled by the residence time in the fluidized bed and is free of dust.

[0090]

Table 2: Composition and properties of granules

Zeolite A: Wessalith P® (a product of Degussa AG) Zeolite X: Wessalith XD® (a product of Degussa AG) ABS: dodecylbenzenesulfonic acid sodium salt: Maranil A 5549 (Henkel KG)
aA, active substance content 55% by weight) used as paste FAS: C ₁₂ -C ₁₈ fatty alcohol sodium sulfate: Texapon LS® (product of Degussa AG) used as paste Amorphous silicate: Sipernat 22 S (registered trademark) (a product of Degussa AG)

In the case of Examples E4 and E5 and Comparative Example C1, their particle size distribution was measured directly by discharge from the fluidized bed and coarse particles were not removed by the sieve. In other examples and comparative examples, coarse particles were removed by sieving.

The granules produced according to the invention can all be handled and rapidly dissolve without exhibiting stickiness and without loss of flowability.

Comparative Example C1 is a high surfactant content granule prepared under the above conditions, which contains a zeolite A carrier and exhibited fluidity. Inventive Examples E4 and E5, prepared under the same conditions, showed comparable flow properties, despite having a high surfactant content of over 20%.

To determine the solubility behavior of compounds E10 and C2 (L test), test granules
Disperse 8 g in a 2 L glass beaker with stirring (800 rpm, laboratory stirrer, stirrer head 1.5 cm from bottom in center of glass beaker) and 30 minutes at 30 ° C. Stirred. The test was performed using water having a hardness of 16 ° d. The wash liquor was then poured into an 80 μm sieve. The glass beaker was washed on the sieve with a small amount of cold water. The measurement was performed twice. The sieve was dried in a drying cabinet at 40 ± 2 ° C. to constant weight and the residue weighed. Example E
The residue of 10 is 7% by weight, while the residue of comparative example C2, which has a lower surfactant content, especially less fatty alcohol sulphate, is 32% by weight.

The flowability of the compounds E8 and E9 according to the invention is comparable to that of the commercial surfactant compounds with a high surfactant content and a sodium sulphate carrier (Comparative Examples C3 to C3 of Table 3).
C5) was tested by a lump test. For this test, one
5 ml of the compound was weighed into a 25 ml measuring cylinder and transferred to a stainless steel cylinder standing in a porcelain dish. A stainless steel pestle was then inserted into the cylinder without compressing the powder and a weight of 500 g was applied. After 30 minutes and 24 hours, the weight was removed, the cylinder was lifted, and the plug was extruded with a pestle. The test was performed at room temperature and 40 ° C. If the plug collapses upon extrusion, the lamp test score is 0. If not, the container was placed in the dish containing the plug and water was poured until the plug collapsed.
Table 4 shows the amount (g) of water required for the collapse as a rating of the lamp test.

[0097]

[Table 3]: Composition of Comparative Example (commercial product)

[0098]

[Table 4]: Lamp test results (amount of water required for plug collapse)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat 参考 (Reference) C11D 17/06 C11D 17/06 (72) Inventor Dieter Jung D-40723 Hilden, Am Eichhe, Federal Republic of Germany Lukamp 199 (72) Inventor Olaf Brochowitz Federal Republic of Germany Day-39307 Genting, Lorenzstrasse No. 4 (72) Inventor René Andres Artiga-Gonzales Federal Republic of Germany Day-40589 Dusseldorf, Einsteinstrasse 5th F term (reference) 4G004 AA02 KA01 4H003 AB19 AB27 BA10 BA17 CA20 EA15 EA16 EA28 FA32 FA41

Claims (11)

[Claims] 1. Soluble surfactant granules suitable as additives in detergent compositions and / or detergent compositions, said soluble surfactant granules comprising 55 to 95% by weight of anionic surfactant And 5-3
A granule comprising 0% by weight of faujasite-type zeolite. 2. In addition to the sulfonate type anionic surfactant, the granules are
C ₁₂ -C ₁₈ alkyl sulfates, especially, include a C ₁₂ -C ₁₄ alkyl sulfates, the sulfonate surfactant weight ratio of the sulfuric ester type surfactant,
2. Granules according to claim 1, wherein the granules are from 1: 1 to 20: 1, in particular from 2: 1 to 10: 1. 3. The granules contain less than 7% by weight of water, especially when the surfactant content is more than 70% by weight,
2. The granule according to claim 1, comprising less than wt% water. 4. The faujasite-type zeolite is zeolite X.
4. The granule according to any one of claims 1 to 3. 5. The method according to claim 1, wherein the faujasite-type zeolite is used in an excessively dried form, and the water content of the zeolite which can be removed at 800 ° C. is smaller than the equilibrium water content of the zeolite used. The granules according to the above. 6. The granules are an alkali metal carbonate, preferably sodium carbonate,
In particular, including calcined sodium carbonate, the weight ratio of alkali metal carbonate: faujasite type zeolite is 5: 1 to 1: 5,
The granule according to any one of claims 1 to 5, wherein the ratio is preferably 2: 1 to 1: 3. 7. A process for producing soluble surfactant granules suitable as an additive in detergent compositions and / or detergent compositions, comprising a water-containing paste of at least one surfactant or surfactant precursor. Together with the inorganic carrier component, preferably simultaneously, and granulating and drying. The liquid components are introduced into the granulating chamber after mixing, or sprayed separately and independently from each other. A faujasite-type zeolite as an inorganic carrier component. 8. An acid of an anionic surfactant is used as a precursor of a surfactant, and an alkaline aqueous solution is used for neutralization of the spray, and the spray neutralization is performed simultaneously with the granulation. 9. The method of claim 7, wherein the method comprises: 9. The method according to claim 7, wherein the method is performed by a fluidized bed. 10. The faujasite type zeolite is used in an over-dried form, the water content of the zeolite which can be removed at 800 ° C. is smaller than the equilibrium water content of the used zeolite, and the faujasite type zeolite is over-dried. Is carried out preferably immediately before granulation. 11. A detergent composition and / or a detergent composition comprising at least one soluble surfactant granule and another component, wherein the soluble surfactant granule is a composition according to any one of claims 1 to 6. A granule according to any one of claims and claim 7.
11. A composition, which is a granule selected from the group consisting of a target product obtained by the method according to any one of claims to 10.