JP3009470B2 - Detergent composition - Google Patents

Abstract

There is provided a low temperature process for washing laundry in a domestic washing machine and detergent compositions suitable for use in such a process. In the process of the invention an effective amount of a laundry detergent composition is introduced into the wash liquor during the wash and the process is conducted at a temperature of no more than 50 DEG C, the laundry preferably comprising hydrophobic materials such as polyester or polycotton. The detergent composition comprising an alkali metal percarbonate and one or more non-ionic cellulose derivatives. The washing process of the invention leads to improved whiteness benefits and reduced dispensing problems when compared with processes in which detergent compositions are used which contain perborate as a bleaching agent instead of percarbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low temperature process for washing laundry in a home washing machine and a detergent composition comprising an alkali metal percarbonate and a nonionic cellulose derivative suitable for use in such a process. Nonionic cellulose derivatives, particularly cellulose ethers, are known to be useful as redeposition inhibitors. They are particularly useful for preventing redeposition of greasy stains on hydrophobic fabrics such as polyester or polycotton. The redeposition is based on the release coating of a nonionic cellulose derivative on a hydrophobic fabric.
It is believed that the formation of g) is at least partially prevented.

It is known to provide laundry detergent compositions that incorporate an inorganic perhydrate salt as a source of oxygen bleach. The most widely used inorganic perhydrate bleach in laundry detergent compositions is sodium perborate in the form of monohydrate or tetrahydrate.

It is believed that perborate releases borate ions upon dissolution in water, and that these borate ions can form ionic complexes with α (vicinal) -diols such as cellulose derivatives. Such ionic complexes have a higher solubility than uncomplexed cellulose derivatives and prevent their deposition on hydrophobic fabrics. This has impaired the realization of shine by preventing redeposition of oil stains, and it has been found that it is often necessary to increase the percentage of cellulose derivatives in the detergent composition to achieve satisfactory performance.

It is desirable to keep the levels of cellulose derivatives to a minimum because of cost reasons and higher levels can cause distribution and formulation problems.

 According to the present invention, there is provided a laundry detergent composition comprising (a) an alkali metal percarbonate (b) one or more nonionic cellulose derivatives.

According to the present invention, there is also provided a method of washing the laundry, preferably in a home washing machine, wherein an effective amount of the laundry detergent composition of the present invention is put into the washing liquid during washing, and the process is performed at a temperature of 50 ° C or less. You. Preferably, the nonionic cellulose derivative remains substantially nonionic during washing.

Detergent compositions containing percarbonate and cellulose derivatives were found to exhibit better anti-redeposition and whiteness / brightness performance than detergent compositions containing perborate and cellulose derivatives or cellulose derivatives alone. . The percarbonate does not appear to interfere with the deposition of the cellulose derivative on the hydrophobic fabric. This is probably because percarbonate does not cause ionization of the diol in the cellulose. Irrespective of the mechanism, it is surprising that the use of percarbonate instead of perborate reduces the level of cellulose derivatives in the detergent composition to reduce distribution problems or to obtain good anti-redeposition properties. Is also possible.

The nonionic cellulose derivative is preferably a cellulose ether. Particularly useful cellulose ethers according to the present invention include hydroxyethyl cellulose,
There are hydroxypropylcellulose, methylcellulose and mixtures thereof. Hydroxyethyl cellulose is particularly preferred.

It is desirable that the nonionic cellulose derivative be present in the detergent composition in as low an amount as possible while maintaining sufficient anti-redeposition and whiteness performance. It is usually less than 3% by weight of the total composition, preferably less than 1.5% by weight of the total composition,
More preferably, it is present in an amount of 1% or less.

The alkali metal percarbonate used is preferably sodium or potassium percarbonate, more preferably sodium percarbonate. Percarbonate is usually in particulate form. The percarbonate particles usually have an average particle size of 150 to 1200 μm, preferably 300 to 900 μm. The percarbonate particles may be coated or uncoated. If they are coated, this is preferably a water-soluble coating. Suitable coating materials are alkali or alkaline earth metal carbonates; alkali or alkaline earth metal sulfates; sulfuric acid and mixed salts of alkali or alkaline earth metals; chlorides and mixed salts of alkali or alkaline earth metals; nitric acid and There are mixed salts of alkali carbonates or alkaline earth metals. Suitable coatings are described in GB 1,466,799 along with the coating process.

The percarbonate is present in the detergent composition in any of the conventionally used proportions. The effect of the present invention is particularly demonstrated in compositions containing a large proportion, for example, 9% by weight or more of oxygen releasing bleach. It is advantageous to replace perborate with percarbonate, and the effect of the present invention is percolated because perturbation of performance has been found to be particularly pronounced in compositions containing a high proportion of perborate. This is particularly felt in equivalent formulations containing. Thus, the advantages of the present invention are most pronounced in compositions containing percarbonate in an amount of 9% by weight or more of the total composition.

In the process of the present invention, the nonionic cellulose derivative appears to remain substantially nonionic throughout the wash. Some very small amounts of ionization may occur spontaneously upon introduction of the cellulose derivative into the wash liquor. However, the degree of such ionization is extremely small, and the concentration of the ionized cellulose derivative generated in the washing solution is also extremely small. Ionization does not occur to the extent seen when perborate bleach or other sources of borate ions are introduced into the wash liquor.

The process of the present invention is performed at a temperature below 50 ° C. The reaction is preferably performed at a temperature of 45 ° C or lower, more preferably 40 ° C or lower, and most preferably 10 to 35 ° C.

The process of the present invention is particularly effective when the laundry comprises synthetic fabrics, including hydrophobic fabrics such as polyester and polycotton.

The granular laundry composition according to the present invention comprises from 1 to 40%, preferably from 2 to 15%, most preferably from 3 to 10% by weight of the composition from peroxyacid bleach precursors, organic peroxyacids and mixtures thereof. An optional additional bleach may be included.

The peroxyacid bleach activators (bleach precursors) as additional bleaching components according to the invention can be selected from a wide variety and are preferably those having one or more N- or O-acyl groups.

Suitable classes include anhydrides, esters, amides and acylated derivatives of imidazoles and oximes, examples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred type is GB-A-836 988,
864 798, 1 147 871 and 2 143 231 with esters as disclosed in GB-A-855 735 and 1 24
6 338 is an amide as disclosed in the specification.

Particularly preferred bleach activators as additional bleaching components according to the invention are N, N, N ', N'-tetraacetylated compounds of the formula: In the above formula, x is 0 or an integer of 1 to 6.

Examples are x = 1 tetraacetylmethylenediamine (TAMD), x = 2 tetraacetylethylenediamine (TAED) and x = 6 tetraacetylhexylenediamine (TAHD). These and similar compounds are GB-A-90
7 356. The most preferred peroxyacid bleach activator as the additive bleaching component is TAED.

Another preferred class of peroxyacid bleach activator compounds are amide substituted compounds of the general formula: Wherein R ¹ is an aryl or alkaryl group having from about 1 to about 14 carbon atoms; R ² is an alkylene, allylene and alkarylene group having from about 1 to 14 carbon atoms; R ⁵ is H or carbon atom An alkyl, aryl or alkaryl group having 1-10; L is essentially any leaving group. R ¹ is preferably from about 6 to 12 carbon atoms. R ² is preferably about 4 to 8 carbon atoms. R ¹ may be straight or branched alkyl, substituted aryl or alkylaryl with a branched substituent, or both, and may be derived from synthetic sources or natural sources including, for example, tallow. Similar structure variations observed in R ^2. Substituents include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not have more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0 170 386.

Other peroxyacid bleach activator compounds include, for example,
There are sodium nonanoyloxybenzenesulfonate, sodium trimethylhexanoyloxybenzenesulfonate, sodium acetoxybenzenesulfonate and sodium benzoyloxybenzenesulfonate as disclosed in EP-A-03419476.

The compositions of the present invention also include portions commonly found in laundry detergent products.

A wide range of surfactants can be used in the detergent composition. A typical list of anionic, nonionic, amphoteric and zwitterionic classes and types of these surfactants is provided in US Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. A list of suitable cationic surfactants can be found in USP 4,25, issued to Murphy on March 31, 1981.
It is shown in the 9,217 specification.

A mixture of anionic surfactants, especially sulfates,
Blends of sulfonate and / or carboxylate surfactants are suitable for the present invention. Mixtures of sulfonate and sulfate surfactants are usually used in a weight ratio of sulfonate to sulfate of 5: 1 to 1: 2, preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1.

Preferred sulfonates, 9-15 alkyl group, and alkyl benzene sulfonates having especially 11 to 13 carbon atoms, fatty acids C ₁₂ -C ₁₈ fatty source, preferably C ₁₆ -C ₁₈
There are α-sulfonated methyl fatty acid esters derived from fat sources. In each case, the cation is an alkali metal, preferably sodium. Preferred sulphate surfactants in such sulphonate sulphate mixtures are alkyl sulphates having 12 to 22, preferably 6 to 18 carbon atoms in the alkyl group. Another useful surfactant system consists of a mixture of two alkyl sulphate substances, each with a different average chain length. One such system is 3: 1 to 1: 1 of C ₁₄ -C _15: a mixture of C ₁₄ -C ₁₅ alkyl sulfates and C ₁₆ -C ₁₈ alkyl sulfates in the weight ratio of C ₁₆ -C ₁₈ . The alkyl sulfates may be combined with alkyl ethoxy sulfates having from 10 to 20, preferably from 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of from 1 to 6. The cation in each case is also an alkali metal, preferably sodium.

Another anionic surfactant suitable for the purpose of the present invention is an alkali metal sarcosinate of the formula: R-CON (R ¹ ) CH ₂ COOM where R is a C ₉ -C ₁₇ linear or branched alkyl. Or an alkenyl group, R ¹ is a C ₁ -C ₄ alkyl group, and M is an alkali metal ion. Preferred examples are lauroyl take the form of a sodium salt, cocoyl (C ₁₂ -C _14), myristyl and oleyl methyl sarcosinates.

One type of nonionic surfactant useful in the present invention is a condensate of ethylene oxide and a hydrophobic moiety, provided that the surfactant is 8 to 17, preferably 9.5 to 13.5, more preferably 10 to 12.5. It has an average hydrophilic-lipophilic balance (HLB) within the range, and the hydrophobic (lipophilic) portion may be aliphatic or aromatic in nature. Particularly preferred nonionic surfactants of this type are C ₉ -C ₁₅ primary alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per mole of alcohol, especially C ₁₄ -C ₁₄ containing 6 to 8 moles of ethylene oxide per mole of alcohol. -C and ₁₅ primary alcohol, a C ₁₂ -C ₁₄ primary alcohols containing ethylene oxide per mole of alcohol 3-5 mol.

Another preferred class of nonionic surfactants comprises polyhydroxy fatty acid amides of the general formula: Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R ² is C ₅ -C ₃₁ hydrocarbyl; Z is linear hydrocarbyl and Polyhydroxyhydrocarbyl having at least three hydroxy groups directly attached to the chain or an alkoxylated derivative thereof. For a preferred substance of this type, the polyhydroxyhydrocarbyl moiety is derived from glucose, maltose or a mixture thereof, and R ²
The groups are C ₁₁ -C ₁₉ alkyl or alkenyl moieties such as R ¹ groups. Compositions incorporating such highly preferred polyhydroxyfatty acid amides are disclosed in co-pending UK Application No. 9113139, filed June 18,1991.

Another type of nonionic surfactant consisting of an alkyl polyglucoside compounds of the following general _{formula: RO (C n H 2n O} ) t Z x above formula Z is a moiety derived from glucose; R
Is a saturated hydrophobic alkyl group containing 12-18 carbon atoms; t is 0-10; n is 2 or 3; x is 1.3-4; 50% with alcohol
It contains the following short-chain alkyl polyglucosides: Compounds of this type and their use in detergent compositions are EP
B0070074, 0070077, 0075996 and 0094118.

Another type of surfactant is a semi-polar surfactant such as an amine oxide. Suitable amine oxides are the mono C ₈ -
C _20, preferably selected from C ₁₀ -C ₁₄ alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides (remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl group).

Cationic surface active agents also can be used in the present detergent compositions, quaternary ammonium surfactants suitable mono C ₈ -C _16, preferably C ₁₀ -C ₁₄ N-alkyl or alkenyl ammonium surfactants (remaining N Position is substituted with a methyl, hydroxyethyl or hydroxypropyl group).

Detergent compositions generally comprise from 3 to 35% by weight of the composition, more usually from 5 to 25% by weight, more preferably from 10 to 25% by weight.
Contains a surfactant.

Preference is given to combinations of surfactant types, more particularly anionic-nonionic and anionic-nonionic-cationic blends. A particularly preferred combination is GB-A-2040
987, GB9113139 and EP-A-0087914. Although the surfactants can be incorporated into the composition as a mixture, it is preferred to control the point of addition of each surfactant to optimize the physical characteristics of the composition and avoid processing problems. The preferred mode and order of surfactant addition is described below.

The granular detergent composition according to the invention preferably also contains one or more detergent builders, most preferably detergent builders, including non-phosphate detergent builders. It is preferred that the detergent composition as a whole does not contain phosphoric acid. These include alkali metal carbonates, bicarbonates, calcium carbonate, calcium bicarbonate, silicates, aluminosilicates, monomeric and oligomeric polycarboxylates, homo- or copolymer polycarboxylic acids or salts thereof (polycarboxylic acids having no more than 2 carbon atoms). And at least two carboxylic acid groups separated from each other), and mixtures of any of the foregoing, but are not limited thereto. The builder system is composed of 1 to
80% by weight, preferably 25-60% by weight, more preferably 30%
It is present in an amount of 6060% by weight.

Suitable silicates have a SiO ₂ : Na ₂ O ratio in the range of 1.6: 3.4, with so-called amorphous silicates having a SiO ₂ : Na ₂ O ratio of 2.0: 2.8 being preferred. These materials are, for example, as a slurry of the components to be spray dried, in the form of an aqueous solution that acts as a flocculant for the other solid components, or as a solid in the other particulate components of the composition when the silicate itself is in particulate form. It can be added at various points in the manufacturing process. However, for compositions in which the percentage of the spray-dried component is low, ie, 30%, it is preferred that the spray-dried component contain an amorphous silicate.

Highly preferred materials within the type of silicate is a crystalline layered sodium silicate of the general _{formula: NaMSi x O 2x + 1 ·} yH 2 O above wherein M is sodium or hydrogen, x is 1.9 to
And y is a number from 0 to 20. Crystal-stacked sodium silicates of this type are disclosed in EP-A-0164514 and their preparation is described in DE-A-3417649 and D-A-3417649.
It is disclosed in the specification of EA-3740423. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4, and is preferably 2. More preferably, M is sodium and y is 0; preferred examples of this formula include α, β, γ
And δ-form Na ₂ Si ₂ O ₅ . Each of these substances NaSKS
-5, NaSKS-7, NaSKS-11 and NaSKS-6 are commercially available from Hoechst AG FRG. The most preferred material is _{Na 2 Si 2 O 5, NaSKS} -6. The crystal-laminated silicate is blended as a dry mix solid or as a solid component of an aggregate with other components.

A range of aluminosilicate ion exchange materials can also be used, and preferred sodium aluminosilicate zeolites have the following unit cell formula: Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] xH ₂ O where z and y Is at least 6, the molar ratio of z to y is 1.0 to 0.5, and x is at least 5, preferably 7.
It is 5-276, more preferably 10-264. The aluminosilicate material is in a hydrated form, preferably in bound form
%, More preferably 18 to 22% water.

The aluminosilicate ion exchange material is 0.1 ~ 10μ
m, preferably a particle size of 0.2-4 μm. As used herein, the term "particle size" refers to the average particle size of a given ion exchange material as determined by conventional analytical techniques such as microscopy using a scanning electron microscope or a laser granulometer. Aluminosilicate ion exchange material is further characterized by their calcium ion exchange capacity, which is at least 200mg equivalent of CaCO ₃ water hardness / g aluminosilicate was calculated on a dry basis,
Usually it is in the range of 300-352 mg eq / g. The aluminosilicate ion exchange materials of the present invention are further characterized by their calcium ion exchange rate, which is based on at least 130 mg equivalents of CaCO ₃ // min /
(G /) [2glen Ca ⁺⁺ / gal / min / (g / gal)] aluminosilicate (anhydrous base), usually 130mg equivalent of CaC
O ₃ // min / (g /) [2g / gal / min / (g / gal)] to 390mg equivalent of CaCO ₃ // min / (g /) [6g / gal / min / (g / gal )] Range. The best aluminosilicate for builder purposes is at least 260mg equivalent of C
aCO ₃ // Indicates a calcium ion exchange rate of min / (g /) [4g / gal / min / (g / gal)].

Aluminosilicate ion exchange materials useful in the practice of the present invention are commercially available, some are natural, but are preferably synthesized. How to make aluminosilicate ion exchange material
It is described in US Pat. No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are commercially available under the names zeolite A, zeolite B, zeolite P, zeolite MAP, zeolite X, zeolite HS and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is zeolite A and has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O where x is 20-30, especially 27. Formula Na ₈₆ [(Al
O ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] · 276H ₂ O zeolite X and the formula Na ₆
[(AlO ₂ ) ₆ (SiO ₂ ) ₆ ] · 7.5H ₂ O zeolite HS is also suitable.

Suitable water-soluble monomeric and oligomeric carboxylate builders can be selected from a wide range of compounds, such compounds having a primary carboxyl logarithmic acidity constant (pK ₁ ) of 9 or less, preferably 2 to 8.5, more preferably 4 to 7.5. It is preferable to have

The log acidity constant is defined for the following equilibrium: In the above formula, A ⁻ is a monovalent ionizing anion of the carboxylate builder salt.

Thus, the equilibrium constant for a dilute solution is: And represented by the pK ₁ = log10K _1.

For the purposes of this specification, the acidity constant is defined at 25 ° C. and zero ionic strength. Taken if literature values are available (Stability Constants of Metal-Ion Complexes, Spec
ial Publication No. 25, the Chemical Society, London
See also: if in doubt, they are examined by potentiometric titration with a glass electrode.

The carboxylate or polycarboxylate builder may be monomeric or oligomeric in type, but monomeric carboxylate is usually preferred for cost and performance reasons.

The monomer and oligomer builders can be selected from acyclic, cycloaliphatic, heterocyclic and aromatic carboxylates having the general formula: Wherein R ₁ is H, optionally hydroxy, carboxy,
Represents a C _1-30 alkyl or alkenyl substituted by a sulfo or phosphono group or attached to a polyethyleneoxy moiety containing up to 20 ethyleneoxy groups; R ₂ is H, C
_{1-4 represents} an alkyl, alkenyl or hydroxyalkyl, or alkaryl, sulfo or phosphono group; X represents a single bond, O, S, SO or NR ₁ ; Y is H, carboxy, hydroxy, carboxymethyloxy, or C optionally substituted with a hydroxy or carboxy group
_1-30 alkyl or alkenyl; Z represents H or carboxy; m is the integer of 1 to 10; n is a integer from 3 to 6; p, q is an integer of 0~6, p + q is 1-6; X,
Each of Y and Z has the same or different designation when repeated in a given molecular formula, and at least one Y or Z in the molecule contains a carboxyl group.

Suitable carboxylates containing one carboxy group include Belgian Patent Nos. 831,368, 821,369 and 821,
There are lactic acid, glycolic acid and their ether derivatives as disclosed in US Pat. Polycarboxylates containing two carboxy groups include succinic acid, malonic acid,
Water-soluble salts of (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and the ethers described in German Offenlegungsschrift 2,446,686 and 2,446,687 and US Pat. No. 3,935,257 Carboxylates include the sulfinylcarboxylates described in Belgian Patent 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconicates and succinate derivatives, such as carboxymethyloxysuccinate described in GB 1,379,241, GB 1,389,732. Of the described lactoxysuccinate, the aminosuccinate described in Netherlands Application No. 7205873, and the 2-oxa-1,1,3-propanetricarboxylate described in GB 1,387,447. There are such oxypolycarboxylate materials.

Carboxylates containing four carboxy groups include oxydisuccinates disclosed in GB 1,261,829 and 1,2,2-ethanetetracarboxylate,
1,1,3,3-propanetetracarboxylate and 1,1,2,3
-Propane tetracarboxylate. Polycarboxylates containing sulfo substituents include GB 1,398,
The sulfosuccinate derivatives disclosed in U.S. Pat.Nos. 3,421,421 and 1,398,422 and U.S. Pat.
There is a sulfonated pyrolytic citrate described in 082,179, and polycarboxylates containing a phosphon substituent are disclosed in GB 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadienide pentacarboxylate,
3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3, 4,5,6-hexane-
There are hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the melitic, pyromellitic and phthalic acid derivatives disclosed in GB 1,425,343.

Preferred polycarboxylates among the above are hydroxycarboxylates containing up to 3 carboxy groups per molecule, more particularly citrates.

Mixtures of the monomeric or oligomeric polycarboxylate chelators with the parent acid or salts thereof, such as citric acid or citrate / citric acid mixtures, are also contemplated as components of the builder system useful in the present invention.

Other suitable water-soluble organic salts are homo- or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than 2 carbon atoms. The latter type of polymer is GB-
A-1,596,756. Examples of such salts are polyacrylates of MWt 2000-5000, copolymers of them with maleic anhydride, such copolymers having a molecular weight of 20,000-70,000, especially about 40,000. These materials are usually used at levels of from 0.5 to 10% by weight of the composition, preferably from 0.75 to 8% by weight, most preferably from 1 to 6% by weight.

In a preferred composition, the sodium aluminosilicate, such as zeolite A, is 20-60% by weight of the total builder, the monomer or oligomer carboxylate is 10-30% by weight of the total builder, and the crystal-laminated silicate is 10-65% by weight of the total builders. In such a composition, the builder component includes 35% of all builders.
Preferably, combinations of auxiliary inorganic or organic builders, such as sodium carbonate and maleic anhydride / acrylic acid copolymers, are also included in amounts up to% by weight.

The compositions of the present invention may contain low levels of heavy sequestering agents. The heavy metal ion sequestering agent preferably contained in the detergent composition of the present invention includes aminoalkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxydiphosphonate, nitrotrimethylene phosphonate,
There are organic phosphonates, including ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate. Such phosphonate compounds may exist in their acid form or as a complex of an alkali or alkali metal ion, wherein the molar ratio of the metal ion to the phosphonate compound is at least 1: 1. Such complexes are described in U.S. Pat. No. 4,259,200. Preferably, the organic phosphonate compounds are in the form of their magnesium salts.

Organic phosphonate compounds and mixtures thereof, the composition
It is present in the detergent composition of the present invention at a level of 0.05 to 10%, preferably 0.1 to 2%, most preferably 0.2 to 0.6% by weight.

The composition according to the invention can also contain other optional detergent components. Additional anti-redeposition and soil suspending agents, optical brighteners, soil release agents, dyes and pigments are examples of such optional ingredients and can be added in various amounts as desired.

Anti-redeposition and soil suspending agents suitable for the present invention (besides the previously described cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose) include homo- or copolymer polycarboxylic acids or their salts. Polymers of this type include copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride being at least 20 mol% of the copolymer. These materials usually comprise 0.5-10% by weight of the composition, more preferably 0.75%.
-8% by weight, most preferably 1-6% by weight.

Other useful polymeric substances are polyethylene glycol,
In particular, it has a molecular weight of 1,000 to 10,000, more specifically 2,000 to 8,000, most preferably about 4,000. They are used at a level of 0.20-5% by weight, more preferably 0.25-2.5%. These polymers and the aforementioned homo or copolymer polycarboxylate salts are beneficial in improving whiteness maintenance, fabric ash deposition, and cleaning performance of soil, proteins and oxidative soils in the presence of transition metal impurities.

Preferred fluorescent whitening agents are on the characteristic anionic, examples being disodium 4,4 ¹ - bis- (2-diethanolamino-4-anilino -s- triazin-6-ylamino) stilbene -2: 2 ¹ - di Sulfonate, disodium 4,4 ¹ −
Bis (2-morpholino-4-anilino -s- triazin-6-ylamino) stilbene -2: 2 ¹ - disulphonate, disodium 4,4 ¹ - bis- (2,4-dianilino -s-
Triazin-6-ylamino) stilbene -2: 2 ¹ - disulphonate, monosodium 4 ^1, 4 ¹¹ - bis (2,4-dianilino -s- triazin-6-ylamino) stilbene -
2-sulphonate, disodium 4,4 ¹ - bis [2-anilino-4-(N-methyl--N-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene -2: 2 ¹ - disulphonate disodium 4,4 ¹ - bis (4
- phenyl-2,1,3-triazin-2-yl) stilbene -2: 2 ¹ - disulphonate, disodium 4,4 ¹ - bis [2-anilino-4- (1-methyl-2-hydroxyethylamino ) -s-triazin-6-ylamino] stilbene -2: 2 ¹ - disulfonate and sodium 2 [stilbyl -4 ¹¹ - (naphtho -1 ^1, 2 ^1: 4,5-1,2,3- triazole - 2 ¹¹ -sulfonate.

Soil release agents useful in the compositions of the present invention are conventional copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units in various configurations. Examples of such polymers are disclosed in commonly assigned US Pat. Nos. 4,116,885 and 4,711,730 and EP-A-0272033. EP-A-0
A particularly preferred polymer according to No. 273033 has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 [(T-PO) _2.8 (T-PEG) _0.4 ] T (POH) _0.25 (PEG) ₄₃ CH ₃ ) in the PEG _0.75 above formula _{- (OC 2 H 4) O-} , PO is _{(OC 3 H 6 O),} T
Is (pCOC ₆ H ₄ CO).

Certain polymeric materials, e.g., typically MWt 5000-2000
Zero, preferably 10,000 to 15,000, polyvinylpyrrolidone forms an agent useful in preventing the transfer of labile dyes between fabrics during the washing process.

Another optional ingredient is a suds suppressor exemplified by silicones and silica-silicone mixtures. Silicones are usually represented by alkylated polysiloxane materials, whereas silica is commonly used in finely divided form, exemplified by silica airgel and xerogel and various types of hydrophobic silica. These materials can be formulated as particles, in which case the suds suppressor is advantageously releasably formulated into a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. Alternatively, the foam control agent may be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other components.

As noted above, useful silicone suds suppressors may comprise a mixture of an alkylated siloxane of the type described above and solid silica. Such mixtures are made by depositing silicone on the surface of solid silica. Preferred silicone suds suppressors have a weight ratio of silicone to silanized silica of from about 1: 1 to about 1: 2, thoroughly mixed with a dimethyl silicone fluid having a molecular weight in the range of about 500 to about 200,000, 10%. It is represented by hydrophobic silanized (most preferably trimethylsilanated) silica having a particle size in the range of 2020 nm and a specific surface area of 50 m ² / g or more.

Preferred silicone suds suppressors are disclosed in Bartollota et al., US Pat. No. 3,933,672. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors described in German Patent Application DTOS 2,646,126 published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane / glycol copolymer.

The above foam control agents are usually used at a level of from 0.001 to 0.5%, preferably from 0.01 to 0.1% by weight of the composition.

Preferred methods of compounding include applying a foam inhibitor in liquid form by spray-on to one or more of the main components of the composition;
Alternatively, there is the formation of a foam inhibitor as separate particles that can be later mixed with other solid components of the composition. When blending the foam control agent as a separate particles, contained therein C ₂₀ -C ₂₄ fatty acids, microcrystalline waxes, other foam control agents substances such as high MWt copolymers of ethylene oxide and propylene oxide Without them, which would adversely affect the dispersibility of the matrix. The technique of forming such foam control particles is described in U.S. Pat.
It is disclosed in S Patent No. 3,933,672.

Another optional ingredient useful in the present invention is one or more enzymes.

Preferred enzymatic substances include commercially available amylase, neutral and alkaline proteases, lipases, esterases and cellulases conventionally formulated in detergent compositions. Suitable enzymes are described in US Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include Alcalase and Savinase (Sa) from Novo Industries A / S (Denmark).
vinase) is available from International Bio-Synthetics, Inc. (Netherlands) as Maxatase.

Preferred amylases include, for example, amylases obtained from certain strains of B. licheniforms, which are described in more detail in GB-1,296,839 (Novo). Preferred commercially available amylases include, for example, Rapidase sold by International Biosynthetics and Termamyl sold by Novo Industries.

A particularly preferred lipase enzyme is trade name lipolase (Lipolase).
lase) (Biotechnology Newswatch, 7 March 1988, page
6) manufactured and sold by Novo Industries (Denmark) as EP-A-0258068 (Novo)
And other suitable enzymes.

Fabric softeners can also be included in the laundry detergent composition. These agents may be inorganic or organic in type. The inorganic softener is exemplified by the smectite clay disclosed in GB-A-1,400,898. GB-
There are water-insoluble tertiary amines as disclosed in A-1514276 and EP-B-0011340.

Mono C ₁₂ -C ₁₄ quaternary ammonium salts and combinations and they are disclosed in EP-B-0026527 and 528 herein.
Another useful organic fabric softening agent is a dilong chain amide as disclosed in EP-B-0242919. Additional organic components of the fabric softening system include high molecular weight polyethylene oxide materials such as those disclosed in EP-A-0299575 and EP 0313146.

The level of smectite clay is usually in the range of 5 to 15% by weight, more preferably 8 to 12%, and the substance is added as a dry mix component to the rest of the formulation. Organic fabric softeners such as water-insoluble tertiary amines or di-long chain amide materials are incorporated at levels of 0.5-5% by weight, usually 1-3% by weight, while high molecular weight polyethylene oxide materials and water-soluble cationic The substance is 0.1 to 2% by weight, usually 0.15 to
It is added at a level of 1.5% by weight. If a portion of the composition is spray-dried, these materials can be added to the aqueous slurry fed to the spray-drying tower, but in some cases they can be added as dry mix particles or other components of the composition. It is more convenient to spray them as a molten liquid on the solid components.

A feature of the compositions of the present invention is that they have a relatively high density compared to conventional laundry detergent compositions. Such high-density compositions have become known as concentrated products, at least 650 g /, more usually at least 700 g /
, More preferably with a bulk density of more than 800 g /. Bulk density is simple, consisting of a conical funnel securely mounted on a base and a flap valve at its lower end to empty the funnel contents into a coaxial cylindrical cup placed under the funnel. Measured with a simple funnel and cup device. The funnel is 130 mm high and has an inner diameter of 130 mm and 40 mm at each of its upper and lower ends. It is installed so that its lower end is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an inside diameter of 84 mm. Its nominal volume is 500ml.

To perform the measurement, the funnel is filled with powder by hand pouring, the flap valve is opened, and the powder is filled into the cup. The filled cup is removed from the frame and excess powder is removed from the cup by tracing along the top end with a straight-end tool, for example a knife. The filled cup is then weighed and the value obtained for the weight of the powder is multiplied by 2 to determine the bulk density g /. Repeat measurements are made as needed.

The compositions of the present invention may incorporate at least one multi-component system, ie, they need not be compositions formed simply by dry-mixing all individual components. Compositions in which the individual components are dry-mixed are usually dusty, slowly dissolve, and tend to harden during storage and have poor particle flow properties.

The composition of the present invention is a dry mix, spray dry,
It can be manufactured by various methods, including agglomeration and granulation, the preferred method being a combination of these techniques. The preferred method of producing the composition is a combination of spray drying, agglomeration in a high speed mixer and dry mix.

Preferred detergent compositions according to the invention comprise at least two particulate multi-component systems. The first system comprises at least 15% by weight of the composition, customarily 25-50%, more preferably 35%
Wherein the second system is 1-50% by weight of the composition, more preferably 10-40%.

In a preferred embodiment of the invention, one multi-component system is an agglomerate of non-spray-dried components combined with a second multi-component system consisting of a spray-dried powder.

The first system consists of particles blended with an anionic surfactant in an amount of 0.75-40% by weight of the powder and one or more inorganic and / or organic salts in an amount of 99.25-60% by weight of the powder. . The particles can take any suitable form such as granules, flakes, prills, marumes or noodles, but are preferably granules. The granules themselves may be agglomerates formed by bread or drum agglomeration or in-line mixers, but conventionally a spray made by spraying an aqueous slurry of the components with a stream of hot air to remove most of the water. Dry particles. The spray-dried granules are then subjected to a densification step, for example by a high-speed cutter mixer and / or a compression mill, to increase the density before being re-agglomerated. For illustrative purposes, the first system is described below as a spray-dried powder.

Anionic surfactants suitable for primary purposes include those that dissolve slowly, straight-chain alkyl sulfate salts where the alkyl group has an average of 16 to 22 carbon atoms, and those in which the alkyl group averages
It was found to be a straight chain alkyl carboxylate salt having 16 to 24 carbon atoms.

The alkyl groups for both types of surfactants are preferably derived from natural fats such as tallow. More than 40%
Shorter chain alkyl sulphates or carboxylate from which the alkyl groups are derived from a source consisting of a mixture of alkyl moieties having 14 or less carbon atoms are gel-like masses as they dissolve in the first system. Is not appropriate because

The level of anionic surfactant in the spray-dried powder forming the first system is between 0.75 and 40% by weight, more generally between 2.5 and 25%, preferably between 3 and 20%, more preferably between 5 and 15%. is there. Or it is contained also water-soluble surfactants such as linear alkyl benzene sulfonate or C ₁₄ -C ₁₅ alkyl sulfates, or may be applied to the spray dried powder by later spray-on.

Another major component of the spray-dried powder is one or more inorganic or organic salts that impart a crystalline structure to the granules. The inorganic and / or organic salts may be water-soluble or water-insoluble,
The latter type is constituted by the water-insoluble builder or its main part, which forms part of the builder component. Suitable water-soluble inorganic salts include alkali metal carbonates and bicarbonates. Alkali metal silicates other than the crystal-laminated silicate can also be present in the spray-dried granules, provided that the aluminosilicate does not form part of the spray-dried system.

When the aluminosilicate zeolite forms a builder component or a part thereof, it is preferable that the zeolite is blended in a multi-component system instead of being directly added to another system by dry-mixing. If the incorporation of the zeolite takes place in spray-dried granules, the silicates present must not form part of the spray-dried granules. Under these circumstances, the formulation of the silicate can be done in several ways, for example to make another silicate-containing spray-dried particle,
This can be done by incorporating the silicate into an aggregate of another component, or more preferably by adding the silicate as a dry mix solid component.

The first system can also contain up to 15% by weight of various components such as whitening agents, anti-redeposition agents including nonionic cellulose derivatives, photoactivated bleach and heavy metal ion sequestering agents. If the first system is a spray-dried powder,
It is usually dried to a moisture of 7-11% by weight, more preferably 8-10% by weight of the spray-dried powder. Powders made by other processes such as agglomeration have a lower moisture content, which may be in the range of 1 to 10% by weight.

The particle size of the primary system is customary, preferably less than 5% by weight should be more than 1.4 mm, while less than 10% by weight should be less than 0.15 mm in maximum dimension. Preferably at least 60% by weight, most preferably at least 80% of the powder is between 0.9 and 0.25 mm in size. In the case of spray-dried powders, the bulk density of the particles from the spray-dry tower is conventionally in the range of 540-600 g /, which means that additional processing steps such as size reduction with a high speed cutter / mixer and subsequent compression. Can be enhanced by: On the other hand, processes other than spray drying may be used to directly form high density particles.

A second system of the preferred composition according to the invention is a single multi-component particle containing a water-soluble surfactant.

The water-soluble surfactant may be anionic, nonionic, cationic or semipolar in type, or a mixture of any of these. Although suitable surfactants are the preferred surfactants are C ₁₄ -C ₁₅ alkyl sulfates, linear C ₁₁ -C ₁₅ alkyl benzene sulfonates and fatty C ₁₄ -C ₁₈ methyl ester sulfonate. The second system may have any suitable physical form, that is, it may be in the form of flakes, prills, mrooms, noodles, ribbons or granules, and may be either spray-dried or non-spray-dried agglomerates. The second system may, in theory, itself consist of a water-soluble surfactant, but in practice at least one organic or inorganic salt is included to facilitate processing. They impart some crystallinity and thus acceptable flow properties to the particles and may be any one or more organic or inorganic salts present in the first system.

The size range of the second system is not critical, but should be such as to avoid separation from the particles when blended with the first system. For this reason, less than 5% by weight is 1.4m
m should be greater than 10%, while less than 10%
Should be no more than 5mm.

The bulk density of the second system is a function of its mode of manufacture. However, the preferred form of the second system is a mechanically mixed agglomerate, which may be a bread agglomerator, a Z-blade mixer, or more preferably a Schugi (Holland) BV 29 Chroo.
mstraat 8211 AS, Lelystad, Netherlands and Gebruder L
odige Maschinenban GmbH, D-4790 Paderborn 1, Elsene
rstrasse 7-9, made by adding the dry ingredients to an in-line mixer such as that manufactured by Postfach 2050 FRG or with a flocculant. According to this means, the second system is 650-1190 g /, more preferably 750-850 g.
/ Has a bulk density in the range.

Preferred compositions contain a level of alkali metal carbonate in the second system corresponding to an amount of 3 to 15%, more preferably 5 to 12% by weight of the composition. This is 20 in the second system
Preferably, it exhibits a carbonate level of 4040% by weight.

A highly preferred component of the second system is also a hydrated water-insoluble aluminosilicate ion exchange material of the synthetic zeolite type described above, which is present at 10-35% by weight of the second system. The amount of water-insoluble aluminosilicate material incorporated in this way is 1 to 10% by weight of the composition, more preferably 2 to 8% by weight.

In one process for making the second system, the surfactant salt is formed in situ in an in-line mixer. The surfactant in liquid acid form is added to the mixture of granular anhydrous sodium carbonate and hydrated sodium aluminosilicate in a continuous high speed blender, such as a lodige C6 mixer, and the surfactant salt is maintained while maintaining the granular properties of the mixture. Neutralized to form The resulting agglomerated mixture forms a second system, which is then added to the other components of the product. In a variation of this process, the surfactant salt is preneutralized and added to the mixture of the other components as a viscous paste. In this variation, the mixer simply acts to agglomerate the components to form a second system.

In a particularly preferred process for producing the composition according to the invention, a part of the spray-dried product containing the first granular system is diverted, subjected to a low level of nonionic surfactant spray-on, and then reconstituted with the rest. Blended. The second granule system is made using the preferred process described above.
The first and second systems are then conveyed together with other dry mix components such as carboxylate chelators, sodium percarbonate bleach, bleach activators, soil release polymers, silicates of conventional or crystal-laminated type and enzymes. From which they are transferred to a horizontal rotating drum where the perfume and silicone suds suppressor are sprayed onto the product. In highly preferred compositions, an additional drum mixing step is used in which low levels (about 2% by weight) of finely crystalline material are introduced to increase density and improve granule flow properties. However, this material should not be an aluminosilicate zeolite builder because the zeolite builder present as a separate particle form in the product has been found to have an adverse effect on percarbonate stability.

In a preferred washing process according to the invention, a dispenser containing an effective amount of the granular detergent product is introduced into the drum of the washing machine before the start of the washing cycle. The effective amount of the granular detergent product for use in the processes described herein above depends on the volume and weight of the laundry being washed. The use of 70-150 g of product is typical when the average washing amount is 2-6 kg of soiled laundry on average.

The dispensing device is a container for detergent products used to pour the product directly into the drum of the washing machine. The volume should be such that it can contain enough detergent product as normally used in such a washing process.

Once the laundry is in the washing machine, a dispensing device containing the detergent product is installed inside the drum. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the dispenser is such that it can contain the dry detergent product and release it during the wash cycle in response to agitation as the drum rotates and as a result of its immersion in the wash water. Should.

To release the detergent product during cleaning, the device has several openings through which the product passes. The device, on the other hand, is made of a material that is permeable to liquids but impermeable to solid products, allowing the release of dissolved products. Preferably, the detergent product is released rapidly at the beginning of the wash cycle, thereby providing a temporary localized high concentration product to the drum of the automatic washing machine in this stage of the wash cycle.

Preferred dispensers are reusable and are designed such that the integrity of the container is maintained both in the dry state and during the wash cycle. Particularly preferred dispensing devices for use according to the invention are the following patents: GB-B-2,157,717, GB-B-2,157,718, E
P-A-0201376, EP-A-0288345 and EP-A-0288346
It is described in the specification. J. Bland, Manufacturing Chem
The article published by ist, November 1989, pages 41-46 also describes a particularly preferred dispensing apparatus for granular laundry products of the type commonly known as "granulettes".

Another preferred means of carrying out the process of the present invention is to disperse the composition in a liquid around the fabric in a drum from a reusable dispenser with walls that are permeable to liquids but impermeable to solid compositions. Is to introduce things.

A particularly preferred device of this type is described in EP-A-03
No. 43069 & 0343070. The latter application discloses a device consisting of a flexible sheath in the form of a bag extending from a support ring forming an orifice, the orifice of which provides sufficient product for one cleaning cycle to its back in the cleaning process. Made to fit. Some of the cleaning medium flows into the bag from the orifice, dissolving the product, and then the solution exits from the orifice into the cleaning medium. The support ring is provided with a masking means to prevent the outflow of wet undissolved product, which typically comprises a wall extending radially from the central boss in a spoked wheel arrangement or a similar structure having a helical wall.

Alternatively, the dispensing device may be a flexible container such as a bag or pouch. The bag is a European published patent application
[0018] As disclosed in the specification, it may consist of a fibrous structure coated with a water-impermeable protective material so that the contents can be stored. On the other hand, it is disclosed in European Patent Application Nos. 0011500, 0011501, 0011502 and 001
As disclosed in 1968, it may be formed from a water-insoluble synthetic polymeric material with an edge seal or closure designed to burst in an aqueous medium. A convenient form of water-brittle closure consists of a water-soluble adhesive adhered along one end of a pouch formed from a water-impermeable polymer film, such as polyethylene or polypropylene, to seal it.

The detergent compositions of the present invention are illustrated by the following non-limiting examples, in which all percentages are on a weight basis unless otherwise indicated.

In the detergent composition, the abbreviation component names have the following meanings: LAS: sodium linear C ₁₂ alkyl benzene sulfonate C _16-18 AS: sodium C ₁₆ -C ₁₈ alkyl sulfate C _14-15 AS: sodium C ₁₄ -C ₁₅ alkyl sulfates C _14-15 AE7: 1 mole per average 7 moles of ethylene oxide condensed with C ₁₄ -C ₁₅ primary alcohol C _12-15 AE3: 1 mole per average 3 moles of C ₁₂ -C ₁₅ which is engaged ethylene oxide condensed Primary alcohol TAED: Tetraacetylethylenediamine silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O
Ratio as usual) CMC: Sodium carboxymethyl cellulose Zeolite 4A: Formula Na ₁₂ having a main particle size in 1~10μm range _{(AlO 2 SiO 2) 12 ·} 27H 2 O of hydrated sodium aluminosilicate citrate: trisodium citrate Hydrate MA / AA: 1: 4 maleic acid / acrylic acid copolymer Average molecular weight about 70,000 BASF commercially available, trade name Sokalan CP5 DTPMP: diethylenetriaminepenta (methylene phosphonic acid) Monsanto commercial name, trade name Quest ( Dequest) 2060 Foaming: a mixture of hydrophobic silica and silicone oil Percarbonate: coated with a mixed salt consisting of Na ₂ CO ₃ and Na ₂ SO _{4 in} a molar ratio of 2.5: 1 (CO ₃ / SO ₄ coated Ta) empirical formula 2Na
₂ CO ₃ .3H ₂ O ₂ anhydrous sodium percarbonate bleach (weight ratio of percarbonate: mixed salt = 39: 1, average particle size = 550 μm) Savinase: Proteolytic enzyme sold by Novo Industries, Inc. Lipolase: Novo Industries Lipolytic enzyme sold by the company

Continuation of front page (56) References JP-A-55-27333 (JP, A) JP-A-63-20398 (JP, A) JP-A-63-296690 (JP, A) JP-A-1-85297 (JP) , A) JP-A-2-283800 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/37, 3/39

Claims (14)

(57) [Claims] 1. A laundry detergent composition comprising (a) an alkali metal percarbonate (b) one or more nonionic cellulose derivatives. 2. The detergent composition according to claim 1, wherein the one or more nonionic cellulose derivatives are present in a total amount of up to 3% by weight of the total composition. 3. The detergent composition according to claim 2, wherein the at least one nonionic cellulose derivative is present in a total amount of not more than 1.5% by weight, preferably not more than 1% of the total composition. 4. The detergent composition according to claim 1, wherein the at least one nonionic cellulose derivative is selected from cellulose ethers. 5. The detergent composition according to claim 4, wherein the one or more nonionic cellulose derivatives are selected from hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose and a mixture thereof. 6. The detergent composition according to claim 1, further comprising an additional bleaching agent selected from peroxyacid bleach precursors, organic peroxyacids and mixtures thereof. 7. The detergent composition according to claim 6, wherein the additional bleach is TAED. 8. A composition further comprising a surfactant in an amount of from 3 to 35% by weight of the total composition, wherein the surfactant comprises anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof. The detergent composition according to claim 1, which is selected. 9. A phosphoric acid-free, 1-80% by weight of the total composition
The phosphoric acid-free detergent builder compound of claim 1.
The detergent composition according to any one of claims 1 to 8. 10. The detergent composition according to claim 9, wherein the phosphate-free detergent builder compound is selected from crystal-laminated sodium silicate, zeolites and mixtures thereof. 11. A method for washing laundry in a home washing machine, wherein an effective amount of the laundry detergent composition is introduced into the washing liquid at the time of washing, wherein the process is carried out at a temperature of 50 ° C. or less. A method comprising: (a) an alkali metal percarbonate; and (b) one or more nonionic cellulose derivatives. 12. The process is performed at a temperature of 10 to 35 ° C.
The method according to claim 11. 13. The laundry according to claim 11, wherein the laundry comprises a hydrophobic substance.
Or the method according to 12. 14. The method according to any one of claims 11 to 13, wherein the detergent composition is a composition according to any one of claims 2 to 10.