DK171868B1 - Granular detergent composition - Google Patents

Abstract

Detergent compositions are disclosed which comprise, as a fabric softening ingredient, a fabric softening clay. The fabric softening clay is a hectorite of natural origin, having a layer change distribution such that at least 50% is in the range 0. 23-0. 31 The specified clays have excellent deposition and fabric softening properties.

Description

in DK 171868 B1

The present invention relates to detergent compositions. More specifically, the invention relates to detergent compositions containing a fabric softening amount of hector titles, the clay being in the form of particles having a narrowly defined layer charge distribution.

6B patent specification No. 1,376,379 describes the use of synthetic hectorite clays as anti-repellents. However, there is no mention of a solution to the problem of fabric softening and the use of 10 natural hectorite species is not recommended.

The specification for EP patent application No. 225,142 describes the use of clay materials with certain swellability properties. The application relates exclusively to liquid detergent compositions.

15 In the specification of European Patent Application No. 11,340, the use of a large number of different clay for fabric softening purposes in detergents is described. The clays described are mainly smectite clays, and although hectorite clays are mentioned passively, there is no mention of hectorite clays of natural origin and with the layer loading characteristics required by the present invention.

In the specification of GB Patent No. 1,400,898, detergent compositions containing smectite-type clay are disclosed as detergent compositions. Smectite-type clays with a cation exchange capacity of at least 50 meg / 100 g are considered suitable. Gelwhite GP and Volclay BC, both of which are sodium montmorillonite clays, are described as being preferred because of color and cation exchange capacity.

It is recognized in the detergent industry that the clays disclosed in GB Patent No. 1,400,898 provide substantial fabric softening benefits when used in a detergent. It is also recognized that the sales of these clays on the fabric during the wash operation are far from complete; under typical washing conditions in Europe, less than half of the clay present is actually deposited on the fabric, the remainder being washed away with the washing liquid during subsequent rinsing steps. The softening effect obtained as a result of clay deposition is also affected by factors that are not fully understood.

It is therefore an object of the invention to provide detergent compositions containing a fabric softening clay from which the clay particles are more effectively deposited on the fabric during the washing operation. It is another object of the invention to provide detergent compositions from which the clay particles are effectively deposited, regardless of the builder system used. It is a further object of the invention to select clay materials for use in detergent compositions which provide substantially better fabric softening properties than the clay materials used in commercial softeners to date.

The present invention relates to detergent compositions containing a fabric softening amount of a fabric softening clay. The amount of clay ranges from 1 to 25% by weight of the detergent composition. Said substance softening clay is a hectoral title of natural origin, commonly referred to as trioctahedral smectite.

The clay is present in the form of particles. The particles have a narrowly defined layer charge distribution such that at least 50% of the clay has a layer charge of from 0.23 to 0.31.

Detergent compositions of the invention contain traditional detergent surfactants, conventional detergent builders, and optionally other conventional detergent ingredients. The compositions further contain a fabric softening amount of a fabric softening clay of from 1 to 25% by weight of the detergent composition. The smectite-type clay is selected on the basis of its layer loading properties on 30. The hectorite species of natural origin suitable for the detergent compositions of the present invention have the general formula:

Si4-y “v ° 10 <OH2-zFz> r (X + y) (JLiJi) Mn + n wherein y · = 0, or if y + 0, Me111 is Al, Fe, or B; Mn + is a monovalent (n - 1) or divalent (n - 2) metal ion, e.g. selected from Na, K, Mg, Ca, Sr. The value of (x + y) is the hector title layer's charge. The hectorite species suitable for detergent compositions of the invention have a layer charge distribution such that at least 50% is in the range of 0.23 to 0.31.

Hectorite species of natural origin, with a layer charge distribution such that at least 65% is in the range of 0.23 to 0.31 10 are preferred.

The layer charge distribution in the clay material can be determined using its swelling in the presence of cationic surfactants with specific chain lengths. This approach is described in detail by Lagaly and Weiss in Zeitschrift fur Pflanzenernåhrung und Bodenkunde, 130 (1), 1971, pp. 9-24.

A method has been recently developed for objective assessment of fabric softeners. The process consists of a 20 series of tests known in the detergent industry as the Kawabata KES-F system. The procedure is described in S. Kawabata, "The Standardization and Analysis of Hand Evaluation", 2nd ed., Textile Mach. Soc. of Japan, Osaka, 1980.

It has been found that in particular one of the parameters of the KES-F system, the shear hysteresis parameter 2H65, is useful in the characterization of fabric softening clays. In connection with the present invention, hectorite species which, when incorporated into detergent compositions 1 amount to 10 wt%, are preferred, reduce the shear hysteresis of substances washed therewith by at least 32%, more preferably at least 35%. The displacement hysteresis meter 2H65 is discussed in more detail in Finnimore and Koenig,

Melli and Textile Report 67 (1986) pp. 514-516.

35

Shear hysteresis is determined on cotton terry towels with detergent compositions containing 10% by weight of the clay to be examined. The test is described in more detail in the examples below.

DK 171868 B1 4

Furthermore, the hectorite species used in the detergent compositions are characterized by an unusually high propensity for deposition on fabric. In a standardized test, the composition of the subject clays on substances from a detergent composition is greater than that of traditional smectite types or synthetic hectorite clays. Examples of suitable hectorite species include Bentone EW and Macaloid from NL Chemicals, NJ, and hectoral species from Industrial Mineral Ventures.

10 Other detergent ingredients

Purifying surfactants

Typically, the compositions of the present invention will contain organic surfactants to provide the general cleaning properties associated with the use of such materials.

Purifying surfactants useful in connection with the invention include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical examples of this are all alkyl benzenesulfonates, all alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and all alkyl phenols, amine oxides, α-sulfonates of fatty acids and of fatty acid esters, and the like. are well known from the detergent field. Generally, such cleansing surfactants contain an alkyl group in the range of Cg-Cjg. The anionic cleansing surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the non-ionic 30s generally contain from ca. 5 to approx. 17 ethylene oxide groups. The disclosure of U.S. Patent No. 3,995,669 contains detailed lists of such typical cleansing surfactants. In particular, C Cj-Cj alkyl alkyl benzene sulfonates, C

Also useful as the surfactant in the present compositions are the water-soluble soaps, e.g. ordinary sodium and potassium coconut or tallow soaps which are well known in the art.

The surfactant may comprise as little as 1% of the present composition, but the compositions will preferably contain from 5 to 40%, especially preferably 10 to 30% of the surfactant. Mixtures of the ethoxylated nonionic and anionic agents such as alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred in connection with the removal of a wide range of dirt and stains on clothing during washing. However, very large amounts of non-ionic surfactant have a negative effect on the softening of the clay. Therefore, compositions containing 4% or less of a nonionic surfactant are preferred.

15 Cleaning aids

The composition of the present invention may contain other ingredients which contribute to their cleansing properties. Eg. it is highly preferred that the detergent compositions contain a detergent builder 20 and / or a metal ion sequestrant. Compounds that can be classified and are well known in the art as detergent builders include nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tripolyphosphate and sodium ortho and pyrophosphates, silicates, and mixtures thereof. The metal ion sequestrants include all of the above plus materials such as ethylene diamine tetraacetate, amino polyphosphates (DEQUEST) and a host of other polyfunctional organic acids and salts which are too numerous to be mentioned in detail herein. See the description of US Patent No. 3,579,454 for 30 typical examples of the use of such materials in various detergent compositions. The builder / sequestering agent will generally comprise from ca. 0.5 to 45% of the composition. Particularly preferred are the zeolite builders (eg zeolite A) having a size of 1-10 microns as described in the specification of DE patent no.

35 2 422 655 for use in low phosphate containing compositions.

Particularly suitable phosphate-free builders are ether carboxylate mixtures containing: a) from 1 to 99% of a tartrate monosuccinate component having the structure HOCH - CH - O - CH - CH2 coox coox coox coox wherein X is H or a salt-forming cation; and b) from 1 to 99% by weight of a tartrate monodisuccinate component having the structure CH, - CH - O - CH - CH - O - CH - CH-,

II II II

coox coox coox coox coox coox wherein X is H or a salt-forming cation.

Builder systems of this type are described in more detail in the specification of U.S. Patent No. 4,663,071, issued May 5, 1987 to Busch et al.

20

Typical detergent compositions contain from 5 to 35% of this composition.

Preferably, the washing compositions of the present invention also contain 25 enzymes to improve their cleaning properties against various kinds of dirt and stains during washing. Amylase and protease enzymes suitable for use in detergents are well known in the art and are commercially available as liquid and granular detergents. The commercially purifying enzymes (preferably a mixture of amylase and protease) are typically used in amounts of from 0.001 to 2% and above in the compositions of the invention. Detergent and cellulite enzymes provide both cleansing and softening properties, especially in connection with cotton fabric. These enzymes are highly desirable in the detergent compositions of the invention.

35

The present compositions may contain other ingredients which contribute to their cleaning properties. Eg. advantageously, the compositions may contain a bleaching agent, in particular a peroxyacid bleaching agent. In the context of the present invention, the term DK 171868 B1 7 covers peroxyacetic acid by both peroxyacids as such and systems capable of forming peroxyacids in situ.

The term peroxyacids as such is to be understood as comprising 5 alkali metal and alkaline earth metal salt of the acids. Peroxyacids and diperoxyacids are commonly used; examples of such acids are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.

Systems capable of delivering peracids in situ consist of 10 peroxygen bleach and one activator for this.

The peroxygen bleaches are those capable of delivering hydrogen peroxide in an aqueous solution; these compounds are well known in the art and include hydrogen peroxide, alkali metal peroxides, organic peroxide bleaches such as urea peroxide, inorganic persalt bleaches such as alkali metal perborates, percarbonates, perphosphates, persilicates and the like.

Preferred are sodium perborate which is commercially available in the form of 20 mono- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

The released hydrogen peroxide reacts with a bleach activator to form the peroxyacid bleach. Groups of bleach activators include esters, imides, imdidazoles, oximes and carbonates. Within these groups, preferred materials include methyl o-acetoxybenzoate, sodium p-acetoxybenzenesulfonates such as sodium 4-nonanoyloxybenzenesulfonate, sodium 4-octaoyloxybenzenesulfonate, and sodium 4-decanoyloxybenzenesulfonate, biophenol A -3 ° ethylenediamine, tetraacetylhexamethylenediamine and tetraacetylmethylenediamine.

Other very preferred peroxygen bleach activators described in the disclosures of U.S. Patents Nos. 4,483,778 and 4,539,130 are substituted alkyl or alkenyl esters such as sodium 4- (2-chloro-octanoyloxy) benzenesulfonate, sodium -4- (3,5,5-trimethylhexanoyl-oxy) benzenesulfonate. Suitable peroxyacids also include peroxygen bleach activators as described in published EP Patent Application No. 0 116 571, i.e. compounds of the general type RXAOOH and RXAL, wherein R is a hydrocarbyl group, X is a heteroatom, A is a carbonyl group, and L is a leaving group, especially oxybenzenesulfonate.

Other highly desirable detergent components for use in the present detergent compositions are quaternary ammonium compounds of formula R4R5RgR7N + X ', wherein R 8 to 20, preferably from 12 to 18 carbon atoms, Rg is all alkyl of from 1 to 10 carbon atoms, and Rg and Rj are both C1-C4 alkyl, preferably 10 methyl and X 'is an anion, e.g. chloride. Examples of such quaternary ammonium compounds include Cjg-C ^ alkyl trimethyl ammonium chloride and cocosalkyl trimethyl ammonium methosulfate. The quaternary ammonium compounds can be used in amounts of from 0.5 to 5%.

15

Additional emollients

The detergent compositions of the invention may additionally contain other softening ingredients in addition to the clay material. Examples 20 of suitable constituents are amines of the formula R 1 R 2 R 2 N wherein R 2 is

Cg-Cgo-hydrocarbyl, R₂ is C1-C₂Q hydrocarbyl, and R3 is Cj-C₂Q hydrocarbyl or hydrogen. A preferred amine of this type is di tallow methylamine.

The softening amine is preferably present as a complex with a fatty acid of the formula RC00H wherein R is a C 6 -C 20 - alkyl or alkenyl. It is desirable that the amine / fatty acid complex be present in the form of microfine particles having a particle size in the range of e.g. 0.1-20 microns. These amine / fatty acid complexes are described in more detail in the specification of EP Patent Application No. 0 133 804. Preferred are compositions containing from 1 to 10% of the amine.

Also suitable are complexes of the above-described amine and phosphate esters of the formula DK 171868 B1 9

ISLAND ISLAND

I II

RøO _ _ OH and HO _ P _OH

Wherein Rg and Rg are C C-C CQ alkyl or ethoxylated alkyl groups of the general formula alkyl (OCHCHCH₂) * * wherein the alkyl substituent is Cj-CgQ, preferably Cg-Cjg, and γ is an integer of from 1 to 15, preferably from 2 to 10, most preferably from 2 to 5. Amine / phosphate ester complexes of this type are described in more detail in the specification of EP Patent No. 0 168 889.

Other examples of optional softening ingredients include the softening amides of the formula RjqRjjNCOR2 * wherein Rjg and Rjj are independently selected from the C1-C2 alkyl, alkyl, alkenyl, hydroxyalkyl, aryl and allkyl aryl groups; R 2 is hydrogen or a C 1 -C 6 alkyl or -alkenyl, an aryl or alkyl-aryl group, or O is -R 2 'wherein R 2 is a -C 22 . Preferred examples of these amides are ditalgacetamide and ditalgbenzamide. Good results are obtained when the amides are present in the composition in the form of a composite compound see with a fatty acid or with a phosphate ester, as described above 23 under softening amines.

The amides are present in the composition in an amount of from 1 to 10% by weight.

The amine and amide-softening ingredients can be added to the crutcher mixture and spray dried, or can be added to a detergent granulate as a dry powder, or can be sprayed onto the detergent granule or on a carrier, either in molten or dissolved form. An example of a suitable carrier is perborate monohydrate.

35

The amines disclosed in GB Patent Application No. 2,173,827 are also suitable plasticizers. Particularly suitable are the substituted cyclic amines described therein. Suitable are imidazolines of the general formula 1- (higher alkyl) -amido (lower alkyl) -2- (higher alkyl) -imidazoline, wherein higher alkyl is alkyl having from 12 to 22 carbon atoms and lower alkyl is alkyl having from 1 to 4 carbon atoms. Preferably, plasticizers of this type are added to the composition as particles or agglomerates as described in the specification of European Patent Application No. 265,187.

A preferred cyclic amine is 1-talgamidoethyl-2-talgimidazoline. Preferred compositions contain from 1 to 10% of the substituted cyclic amine.

10

In addition to the ingredients already mentioned, the present compositions may further comprise various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance properties. Typical ingredients include pH regulators, perfumes, dyes, bleaches, optical whites, dirt suspending agents, hydrotropes and gel control agents, freeze-thaw stabilizers, bactericides, preservatives, foam regulators, bleach activators and the like.

In a washing operation, the compositions are typically used at a concentration of at least 500 ppm, preferably 0.10 to 1.5% in an aqueous wash bath at a pH of from 7 to 11 for laundry. The wash can be carried out in the temperature range of from 5 ° C to the boiling point with excellent results.

Industrial application

The detergent compositions of the invention can be formulated as 30 granular or liquid detergents. It has been found that clays with high swelling ability can easily introduce '; in a liquid detergent composition while maintaining phase loss in the unit.

The clay material may be introduced into a liquid detergent composition by mixing, preferably using a high shear rate mixer.

There are several methods for introducing the clay material into a granular detergent.

Eg. For example, the clay may be added to a crutcher blend of conventional detergent ingredients as a powder or as a slurry and a mixture and spray drying may be made to form a detergent granulate.

The clay powder can also be agglomerated to a desirable agglomerate size and then mixed with granules containing the other detergent ingredients. Dry granule clay granules can also be obtained by selecting an appropriate sieve fraction of natural agglomerates, by spraying a clay slurry onto a suitable particulate carrier, by agglomerating clay particles with sodium carbonate, by spray drying a clay slurry, etc.

15

The clay particles may also be introduced into a substrate such as a bag or sheet, optionally with other softening ingredients. Substrates of this type can be added to the laundry together with a conventional detergent.

20

A preferred substrate is a bag containing the clay particles and particles of an alkylamidoalkyl-2-alkylimidazoline of the above type.

Examples I - V

The following granular detergent compositions are prepared: 30

Component Composition (% by weight)

I II III VI V

Benzene sulfate (Na) 7.0 5.0 4.0 1.0 6.5

Tall alcohol sulfate (Na) - 2.0 - 1.0 A-olefin (C C (gJ sulfonate (Na) - 2.0 Number of gallic alcohol ethoxylate (EO₂) 1.0 2.0 2.0 - 0.8

Fatty alcohol (C1-1C) ethoxylate (EO7) - - 6.0

Hydrogenated tallow fatty acid 2.5 1.0 - 1.0 1.0

Coconut fatty acid - - 1.5 - Dodecyltrimethyl ammonium chloride - 1.0 - 1.0

Distearyl methylamine 3.0 ... 3.0

Ditalgbenzamide - 4.0 -

Dodecyldimethyl ammonium num oxide 0.5 - 0.5 - 0.4

Lauryl-Ν, Ν-dimethylamine - - 2.5

Sodium tripolyphosphate 24.0 18 22 32.0

Zeolite 4A - - 20.0

Sodium Nitrilotriacetate - - - - 5.0 Sodium Sulfate 12.4 17.7 15.0 21.3 12.7

Sodium carbonate - 8.0 - 5.0

Sodium silicate 6.0 7.0 4.0 6.0 2.0

Sodium perborate (4aq.) 20.0 15.0 18.0 10.0 18.0

Carboxymethyl cellulose 0.3 0.3 0.5 0.8 0.4 Polyacrylate (etc. 1000-20000) 1.5

Polyacrylate (etc. 4000-5000) - - - - 3.0

Maleic / Acrylic Acid Copolymer (70/30) (etc. 40,000-80,000) 2.0 - 1.5 2.5 Enzymes (protease, amylase, cellulase) 0.6 0.2 0.5 0.5 0.3

Optical white 0.2 0.2 0.3 0.3 0.25

Sulfonated zinc phthalocyanine 30ppm - - 25ppm 25ppm EDTA 0.2 0.2 0.3 0.15 0.2 DK 171868 B1 13

Ethylenediaminetetramethylphosphonic acid 0.2 0.1 - 0.1 0.1

Tetraacetylethylenediamine 1.5 - - - 1.5

Iso-nonanoyloxybenzenesulfonate (Na) 2.0

Silicone / silica foam regulator 0.2 0.15 0.15 0.25 0.2

Perfume 0.25 0.25 0.30 0.2 0.25

Hector Titles * 10.0 7.0 15.0 5.0 10.0 10 Moisture and Other Components _up to 100_ * Concrete EW, a highly purified hectorite from Hector, Canada, marketed by NL Chemicals, NJ. The clay particles are thin and have a length: width ratio of 10: 1 or more (TEM data).

15 Layer charge distribution: more than 65% in the range of 0.23 to 0.31.

The commercial material was treated with a wetting agent. The same material without the wetting agent is also suitable, as is Macaloid (NL Chemicals, NJ), and Hectorite from Hector, CA.

20

To a detergent composition according to Example I, but without clay and distearyl methylamine, various smectitic species were added to an extent of 10%. One sample contained no smectitler, but instead 10%

Sodium sulfate.

25

Each of the compositions was used for the following wash sample: 3 kg of laundry and desired samples (cotton towel towels) * were washed in a commercially available automatic drum washing machine (MIELE W 726) in a wash cycle at 60 ° C. The detergent composition was used at a concentration of 1.12% in water with a hardness of 0.308 g CaCO liter. The laundry was dried on a clothesline at 20 ° C / 65% relative humidity. The samples were instrumentally tested for softness using the Kawabate KES-F system (shear hysteresis at 5 degrees 2HG5 as best correlation parameter with softness of 35 KES-F-1 instrument). The sample size was 20 X 20 cm, with the sample area actually subjected to a shear stress of 20 X 5 cm. From the shear stress curves plotted against the shear angle, the shear hysteresis was calculated at 5 * (2HG5) in N / m.

Each measurement was repeated 8 times to calculate the confidence interval for the DK 171868 B1 14 mean at a 95% confidence level.

Hectorite species of the invention yielded a displacement hysteresis reduction of an average of 40%.

5 2 * Supplier: Santens - Belgium (type Lopez, 340 g / m).

Clothes are washed with the above detergent compositions in the usual manner. The washed fabric is assessed for grip and softness in the Kawabata 10 Evaluation System-Fabric (KES-F; a series of test parameters for measurement parameters that determine the softness and grip of fabrics. For purposes of the invention, shear hysteresis (2HG5) is particularly important. detailed in Melliand Textilbericht §7 (1986) pp. 509-516.

15

Example VI

The following liquid detergent composition is prepared.

Component Composition (% by weight)

Cii_i2 "all cool benzene sulphonic acid 12.0

Fatty alcohol (C12_15) ethoxylate (EO4) 4.0 Coconut fatty acid 10.0

Triethanolamine 6.8

Polyacrylate (1000-20000) 0.5

Enzyme (protease) 0.8

Ethanol 7.0 Polydimethyl siloxane 0.1

Hectorite clay 5.0 1.2 propylene glycol 1.5

Water + minor constituents up to 100.0

As in Examples I-IV

5 DK 171868 B1 15

Examples VII-XI

The following granular detergent compositions are prepared:

Component Composition (weight percent)

VII VIII IX X XI

Na linear C 1-6 alkyl benzene sulfonate - - 17.6

C1-6 linear benzene sulphonate 14.3 7.1 6.8 20.1

NaCl 2 alcohol alcohol sulfate 3.1 7.1 6.8 20.1

Na C 12 alkyl polyethoxylate 6.5 T 1.0 1.1 1.1 STPP - 28.9 27.7 36.9 40.0

Zeolite 4Å 16.5 -

Silicate 6.8 11.0 10.5 5.7 15.2

Carbonate 7.0 - 16.0 14.5 Diethylenetriamine pentacetic acid - 1.2 1.1 - 1.6

Na perborate monohydrate - 4.9 5.0

Sodium Nanoylbenzenesulfonate - 6.8 6.8 Enzyme (protease) 0.3 - -

Hector Titles * 7.5 6.8 4.7 8.9 9.5 1-talgamidoethyl-2-tallow-imidazoline - - - 5.7

Water, sulfate and other ........... the rest up to 100 ............

30 * as in Example I-V 35

Claims (14)

A granular detergent composition containing at least 1% by weight of a detergent surfactant, from 5 to 35% 5 detergent builders, and from 1 to 25% hector titles, characterized in that the hector titles are of natural origin and have the general formula : 10 t <M93-x ^ x> Si4_y Mey Oi0 (OH2.zF2)) - <***> (X + v) Hn * n wherein Me111 is Al, Fe, or B; or y - 0; Mn + is a monovalent (n «1) or divalent (n = 2) metal ion, the clay having such a layer charge distribution (x + y) that at least 50% of the layer charge is in the range ^ of 0.23 to 0.31. Granular detergent composition according to claim 1, characterized in that the hector title has such a layer charge distribution (x + y) that at least 65% of the layer charge is in the range of 0.23 to 0.31. Granular detergent composition according to claim 1, containing from 1 to 25% hector titles, characterized in that the hector titles are of natural origin and that cotton terrycloth cloths washed with a detergent composition containing 10 wt% clay exhibit a shear hysteresis reduction. , 2HG5, of at least 32%. Granular detergent composition according to claim 3, characterized in that the clay provides a shear hysteresis parameter reduction of at least 35%. Granular detergent composition according to any one of the preceding claims, characterized in that it further contains, as an additional plasticizer, from 1 to 10% amine of the formula R 1 R 2 R 3 N, wherein R 2 is C 9 -C 2Q hydrocarbyl, R 2 is Cr hydrocarbyl, and R3 is C1-C4 hydrocarbyl or hydrogen. Granular detergent composition according to claim 5, characterized in that R 1 and R 2 are both alkyls containing from 12 to 18 carbon atoms and R 3 is methyl. Granular detergent composition according to claim 6, characterized in that the amine is present in the form of a complex with a fatty acid of the formula RCOOH, wherein R is a C 6 -C 20 alkyl or alkenyl. Granular detergent composition according to claim 7, characterized in that the amine is present in the form of a complex with a phosphate ester of the formula: o II II RgO Wherein Rg and Rg are C1-C20 alkyl, or ethoxylated alkyl groups of the general formula alkyl- (OCH2CH2) y, wherein the alkyl substituent is C1 "C20 'and y is an electrolyte from 1 ΐιΊ 15 · Granular detergent composition according to any one of the preceding claims, characterized in that it further contains from 1 to 10% of an amide of the formula RjqRjjNCOR2, wherein RjO and Rjj are independently selected from C alkyl, -alkenyl, -hydroxyalkyl, aryl, and alkyl-aryl groups; R 2 is hydrogen or a C 1 -C 4 alkyl or alkenyl, aryl or alkyl aryl group, or is O-R 3, wherein R 3 is a C 1 -C 3 alkyl or 30-alkenyl, a aryl or alkyl-aryl group. Granular detergent composition according to claim 9, characterized in that the amide is present in the form of a compound with the fatty acid according to claim 7. Granular detergent composition according to any one of the preceding claims, characterized in that it further contains from 1 to 10% of a 1- (higher alkyl) amido (lower alkyl) -2- (higher alkylimidazoline, wherein higher alkyl is alkyl having from 12 DK 171868 B1 to 22 carbon atoms and lower alkyl is all carbon having from 1 to 4 carbon atoms. Granular detergent composition according to any of the preceding claims, characterized in that it further contains from 5 to 35% of a builder system, wherein said builder system contains: a) from 1 to 99% by weight of a tartrate monosuccinate component with the structure: HOCH - CH - O - CH - CH, II I - I COQX OOOX OOOX OOOX 15 wherein X is H or a salt-forming cation, and b) from 1 to 99% by weight of tartrate disuccinate component of structure: 20 CH -, -— CH - O - CH - CH - O - CH - CH, I II II OOOX OOOX COOX COOX OOOX COOX wherein X is H or a salt-forming cation. 25 30 35