WO2010124823A1

WO2010124823A1 - Laundry detergent compositions

Info

Publication number: WO2010124823A1
Application number: PCT/EP2010/002531
Authority: WO
Inventors: Matthias Loeffler; Ernesto Iwao Horikoshi; Ana Regina Coimbra; Manlio Gallotti
Original assignee: Clariant International Ltd; Clariant S.A., Brazil
Priority date: 2009-04-28
Filing date: 2010-04-24
Publication date: 2010-11-04
Also published as: MX2011011377A; BRPI1014709A2

Abstract

A laundry detergent composition is described that is present in a solid form and comprises a) one or more cationic surfactant compounds of formula (1) wherein R¹ is C₈-C₂₂-alkyl R² and R³ are — CH₃ groups R⁴ is CH₂CH₂OH and X© is an anion selected from the group consisting of halogens and b) one or more water soluble or water dispersible soil release polymers selected from the group consisting of non-ionic or anionic oligomeric or polymeric esters of aromatic dicarboxylic acids; cellulosic soil release agents and mixtures thereof, and c) one or more anionic surfactants and that is free of phosphate and zeolite builders.

Description

Laundry Detergent Compositions

The present invention relates to laundry detergent compositions present in a solid form and free of phosphate and zeolite builders comprising a quaternary ammonium compound, an anionic surfactant and a soil release polymer that provide same or even better stain removal performance with increased anti- redeposition profile and soap scum dispersion.

Powder laundry detergents, or heavy duty powders (HDP)₁ for household application are complex formulations consisting of surfactants, builders and auxiliary agents (e.g. bleaches, enzymes, processing aids, foam regulators).

Surfactants are responsible for the roll-up and emulsification of oily soils by lowering the oil/water interfacial tension. Among the different types of surfactants, those most commonly used in laundry detergents are anionic surfactants, which are the most sensitive to water hardness. Anionic surfactants are prone to form insoluble salts with calcium and magnesium ions, which are responsible for the water hardness, leaving residues in the clothes and building up as scale in the washing machines.

One of the functions of detergent builders is to support the surfactant action by removing calcium and magnesium ions from the washing liquor and keeping the washing liquor alkaline, enhancing thus the washing performance and anti- redeposition effectiveness (at high pH, both fabric and soil become more negative, increasing mutual repulsion). Sodium tripolyphosphate, zeolites, sodium carbonate and sodium silicate are the most commonly used builders in HDP.

Phosphate builders have been used for many years in HDP as sequestering agents for bivalent ions, mainly Ca²⁺ and Mg²⁺, reducing thus the formation of insoluble salts of these cations and surfactants, such as Linear Alkyl Benzene Sulphonates (LAS), during fabric laundering. The use of phosphate builders, however, is becoming less common due to its environmental profile and many countries have already banned phosphate compounds in detergent formulations. Zeolite builders are commonly used as an option to phosphates but they are water insoluble, compromising the solubility of laundry detergents and causing an undesired deposit on the fabric during washing. It is of common knowledge that the mere removal of the phosphate and zeolite builders from the formulation has negative impact on its performance.

It is widely known that mixtures of anionic and cationic surfactants can present synergistic properties improving properties and performance of domestic, industrial and institutional laundry detergent formulations. The use of cationic surfactants in heavy duty powder formulations improves the removal of clay and fatty soils, graying inhibition, enzyme efficiency and reduces the interference of the surfactant system on the action of dye transfer inhibitors and dye fixing agents. The following patent publications describe the benefits of the use of mixtures of anionic and cationic surfactants for laundry detergent applications: WO 97/42292, WO 98/13451 , WO 98/13452 and WO 98/17755.

The term "soil release agent" is applied to materials that modify the fabric surface minimizing the subsequent soiling and making the cleaning of the fabric easier on further washing cycles. Soil release polymers have been used for many years in laundry detergents compositions. The following patent publications relate to soil release polymers: US 7,160,947, US 4,877,896, US 4,976,879 and US 5,415,807.

It is known in the art that soil release polymers can interact synergistically with cationic compounds improving the soil removal and bleach performance. Synergistic interaction between soil release polymers and surfactants are described in WO 97/42292, WO 97/03162, WO 97/44419 and US 6,004,922.

Now, it has been found that phosphate and zeolite builders can be replaced by a mixture of alkyl hydroxyethyl dimethyl ammonium compounds such as chlorides, anionic surfactants and certain soil release polymers such as, in particular polyesters, keeping the same or having even better stain removal performance and increasing anti-redeposition profile and soap scum dispersion. Thus, the present invention relates to laundry detergent compositions present in a solid form and comprising

a) one or more cationic surfactant compounds of formula (1 )

_R2 _ _N® _ _R3 X© (1)

wherein

R¹ is C₈-C₂₂-alkyl, preferably Cβ-Cu-alkyl and even more preferably

C₈-Cio-alkyl or Ci₂-Ci₄-alkyl R² and R³ are -CH₃ groups R⁴ is CH₂CH₂OH and

X© is an anion selected from the group consisting of halogens, preferably chloride

and

b) one or more water soluble or water dispersible soil release polymers selected from the group consisting of non-ionic or anionic oligomeric or polymeric esters of aromatic dicarboxylic acids; cellulosic soil release agents and mixtures thereof,

and

c) one or more anionic surfactants,

characterized in that the laundry detergent compositions are free of phosphate and zeolite builders. Without to be bound to theory it is believed that the synergistic interaction between the cationic and anionic surfactants and between the cationic surfactant and the soil release polymer compensates the performance loss due to the absence of phosphate and zeolite builders. Also, the soil release polymer prevents the formation of insoluble salts of divalent cations during washing.

Among the soil release polymers according to component b) of the inventive laundry detergent compositions the non-ionic or anionic oligomeric or polymeric esters of aromatic dicarboxylic acids are preferred.

More preferred water soluble or water dispersible soil release polymers according to component b) of the inventive laundry detergent compositions are nonionic or anionic homo- or copolymers of polyethyleneterephtalate (PET) and/or polyoxyethylene-terephtalate (POET).

In a particularly preferred embodiment of the invention the water soluble or water dispersible soil release polymers according to component b) of the inventive laundry detergent compositions are selected from the anionic polyesters described in WO 2007/079850 and WO 2008/110318.

In a further particularly preferred embodiment of the invention the water soluble or water dispersible soil release polymers according to component b) of the inventive laundry detergent compositions have a structure according to the following formula (2)

wherein

R^5a and R^5b independently of one another are polyalkylene glycol monoalkylethers of formula (3)

R6a R6b

I I

(OCH - CH). -O — R⁷ (3)

wherein

R^6a and R^6b independently of one another are -H or C-i-C-iβ n-alkyl or iso-alkyl and preferably any combination of -H and/or a -CH₃ group

R⁷ is a linear or branched C₁-C₃₀ alkyl group or a linear or branched C₂-C30 alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C₆-C₃₀ aryl group or a Ce-C₅₀ arylalkyl group and preferably a -CH₃ group

p is a number of from 1 to 200, preferably of from 1 to 50

R^8a and R^8b independently of one another are -H or -SOsMe, where Me is Li⁺,

Na⁺, K⁺, Mg⁺⁺/2, Ca⁺⁺/2, AI⁺⁺⁺/3, NH₄ ⁺, a monoalkylammonium ion, dialkylammonium ion, trialkylammonium ion and/or tetraalkylammonium ion where the alkyl substituents of the ammonium ions are, independently of one another, (CrC₂₂)-alkyl radicals or (C2-C₁₀)- hydroxy-alkyl radicals; and preferably R^8a and R^8b are -H

R^9a and R^9b independently of one another are -H or Ci-Ci₈ n-alkyl or iso-alkyl and preferably any combination of -H and/or a -CH₃ group

s is a number of from 1 to 200 and preferably of from 1 to 20 and

r and t independently of one another are numbers of from 1 to 100 and preferably of from 1 to 50. In the soil release polymers according to formula (2) the groups indexed with "r" and "t" may have a statistical, random or blockwise distribution and preferably a random distribution.

In a further particularly preferred embodiment of the invention the water soluble or water dispersible soil release polymers according to component b) of the inventive laundry detergent compositions are selected from polymers obtainable by polycondensation of a) aromatic dicarboxylic acids and/or their CrC₄ alkyl esters, b) ethylene glycol, c) 1 ,2-propylene glycol, d) polyethylene glycol with an average molar mass [M_n] of from 200 to 8.000 g/mol, e) C₁-C₄ alkyl polyalkyleneglycol ethers with an average molar mass [M_n] of the polyalkyleneglycol ethers of from 200 to 5.000 and f) a polyfunctional compound, where the molar ratio of the components b), c), d), e) and f), each relating to 1 mol of component a), is of from 0.1 to 4 mol for component b); of from 0 to 4 mol for component c); of from 0 to 0.5 mol for component d); of from 0 to 0.5 mol for component e) and of from 0 to 0.25 mol for component f). In the following these water soluble or water dispersible soil release polymers according to component b) of the inventive laundry detergent compositions are called soil release polymers A.

In preferred soil release polymers A the molar ratio of the components b), c), d), e) and f), each relating to 1 mol of component a), is of from 1.0 to 2.5 mol for component b); 0 mol for component c); of from 0 to 0.4 mol for component d); of from 0 to 0.25 mol for component e) and of from 0 to 0.2 mol for component f).

In more preferred soil release polymers A the molar ratio of the components b), c), d), e) and f), each relating to 1 mol of component a), is of from 1.0 to 2.5 mol for component b); 0 mol for component c); of from 0.1 to 0.3 mol for component d); of from 0 to 0.2 mol for component e) and of from 0 to 0.1 mol for component f).

Preferably component a) used in the polycondensation to prepare the soil release polymers A is terephthalic acid and/or terephthalic acid dimethyl ester.

Preferably the polyethylene glycol d) optionally used in the polycondensation to prepare the soil release polymers A has an average molar mass [M_n] of from 2.000 to 7.000, more preferably of from 5.000 to 6.000 and even more preferably of 6.000.

Preferably the soil release polymers A have a flow factor ffc of more than 8, more preferably of from 10 to 30.

Preferably the soil release polymers A have a melting point of more than 40 ^CC, more preferably of more than 50 ⁰C and even more preferably of more than 55 ⁰C.

Preferably the soil release polymers A have a molecular weight with a peak maximum Mp of from 4.000 to 15.000 g/mol.

An example for a soil release polymer A is TexCare^® SRN 400 which is commercially available from Clariant.

In a further preferred embodiment of the present invention the one or more water soluble or water dispersible soil release polymers of component b) of the inventive compositions that are selected from the group consisting of non-ionic or anionic oligomeric or polymeric esters of aromatic dicarboxylic acids, in particular the soil release polymers that have a structure according to formula (2) given above and the polymers A given above, are selected from non-ionic oligomeric or polymeric esters of aromatic dicarboxylic acids.

Preferably the inventive laundry detergent compositions comprise the one or more cationic surfactant compounds of formula (1 ) and the one or more soil release polymers of component b) in a total amount of from 0.001 to 50 % by weight, preferably of from 0.01 to 20 % by weight and even more preferably of from 0.1 to 5 % by weight, based on the total weight of the inventive laundry detergent compositions, and the weight ratio of the one or more cationic surfactant compounds of formula (1) to the one or more soil release polymers of component b) is of from 50:1 to 1 :50, preferably of from 10:1 to 1 :10 and even more preferably of from 5:1 to 1 :5.

In a particularly preferred embodiment of the invention the inventive laundry detergent compositions are present in a solid form and

a) comprise one or more cationic surfactant compounds of the formula (1 )

R¹

_R2 _ N® _ _R3 X© (1 )

R⁴

wherein

R¹ is C₈-C₂₂-alkyl, preferably C₈-Ci₄-alkyl and even more preferably

C₈-C₁₀-alkyl and/or Ci₂-Ci₄-alkyl R² and R³are -CH₃ groups R⁴ is CH₂CH₂OH and X© is an anion selected from the group consisting of halogens, preferably chloride, and

b) comprise one or more water soluble or water dispersible soil release polymers selected from the group consisting of the soil release polymers that have a structure according to formula (2) given above and the soil release polymers A given above and preferably comprise one or more soil release polymers A given above and

ab) comprise the one or more cationic surfactant compounds of formula (1 ) and the one or more soil release polymers of component b) in a total amount of from 0.001 to 50 % by weight, preferably of from 0.01 to 20 % by weight and even more preferably of from 0.1 to 5 % by weight, based on the total weight of the inventive laundry detergent compositions, where the weight ratio of the one or more cationic surfactant compounds of formula (1 ) to the one or more soil release polymers of component b) is of from 50:1 to 1 :50, preferably of from 10:1 to 1 :10 and even more preferably of from 5:1 to 1 :5

and

c) comprise one or more anionic surfactants,

and

d) are characterized in that they are free of phosphate and zeolite builders.

Preferably, the one or more anionic surfactants according to component c) of the inventive compositions are selected from the group of surfactants consisting of Alkyl Aryl Sulfonates, Alkyl Sulfonates, Alkyl Sulfates, Alkyl Alkoxylated Sulfates, Sulfo Fatty Acid Esters, Salts of Organic Acids (soaps), Sulphosuccinate esters, fatty acid isethionates and taurides, alkyl succinamates, acyl sarcosinates, phosphoric acid esters and salts, acyl glutamates and ether carboxylates.

More preferably, the one or more anionic surfactants according to component c) of the inventive compositions are selected from the group of surfactants consisting of

(a) Alkyl Aryl Sulfonates of the formula

R¹ArSO₃M wherein

R¹ is an alkyl group of from 8 to 18 carbon atoms Ar is a benzene ring and

M is an alkali metal or alkaline earth metal cation, preferably a sodium cation

which may be produced by the sulphonation of alkylbenzenes,

(b) Alkyl Sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, which may be produced by the sulphoxidation of paraffins,

(c) Alkyl Sulfates, i.e. organic esters of sulfuric acid of the formula

ROSO₃M

wherein

R is a Cβ-Ci₈ alkyl or hydroxyalkyl group, preferably a C₁₂-C₁₄ alkyl or hydroxyalkyl group and M is a cation, preferably H, a sodium, potassium, ammonium or substituted ammonium ion or a mixture thereof, the substituted ammonium ion preferably being selected from monoalkylammonium ions, dialkylammonium ions, trialkylammonium ions and quaternary ammonium ions such as tetraalkylammonium ions where the alkyl substituents of the ammonium ions are, independently of one another, (Ci-C₂₂)-alkyl radicals or (C₂-Ci₀)- hydroxy-alkyl radicals, e.g. methyl or ethyl ammonium ion, dimethyl or diethyl ammonium ion, trimethyl or triethyl ammonium ion or tetramethyl ammonium ion,

(d) Alkyl Alkoxylated Sulfates of the formula

R - O - (A)_m - (B)_n - SO₃M wherein

R is a C₈-C₂₄, preferably a C₁₀-C1₈ or even more preferably a C12-C14 alkyl or hydroxyalkyl group

A is -(C₂H₄-O)-

B is -(C₃H₆-O)- n is a number of from O to 20 m is a number of from 0 to 20 (m + n) ≠ 0, preferably 3 < (m + n) ≤ 7 and

M is H or a metal cation, preferably a cation from an alkali metal, or an ammonium cation or a substituted ammonium cation,

(e) Sulfo Fatty Acid Esters of the formula

R¹ - CH(SO₃M)CO₂R²

wherein

R¹ is an alkyl group with an average chain length of from 6 to 22 carbon atoms, preferably of from 8 to 16 carbon atoms

R² is an alkyl group of from 1 to 8 carbon atoms, preferably of from 1 to 4 carbon atoms and M is an alkali metal or alkaline earth metal cation or a mixture thereof, preferably a sodium, potassium, lithium, magnesium or calcium cation or a mixture thereof and more preferably a sodium cation,

(f) Salts of Organic Acids (soaps) produced by the neutralization (saponification) of fatty acids derived from animal, vegetable or synthetic sources with bases. Commercial fatty acids derived from natural sources are normally mixtures of fatty acids of various chain lengths and unsaturation degrees and mainly even numbered. The most commonly used fatty acids for this invention are derived from tallow, coconut, palm kernel and babacu oils. Preferred soaps are those with an organic carbon chain of from 8 to 24 carbon atoms and more preferably of from 12 to 18 carbon atoms. Preferred bases are bases of alkali metals (sodium and potassium preferred) and amines, such as triethanolamine, or

(g) Sulphosuccinate esters, fatty acid isethionates and taurides, alkyl succinamates, acyl sarcosinates, phosphoric acid esters and salts, acyl glutamates and ether carboxylates.

Additional anionic surfactants not specifically mentioned above may also be used in the inventive laundry detergent compositions.

In a preferred embodiment of the inventive compositions the one or more anionic surfactants are selected from the group consisting of Alkyl Aryl Sulfonates, Alkyl Sulfonates, Alkyl Sulfates and Alkyl Alkoxylated Sulfates.

In a more preferred embodiment of the inventive compositions the one or more anionic surfactants are selected from Alkyl Aryl Sulfonates given under (a) above.

Preferably the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 50 % by weight, preferably of from 5 to 30% by weight and more preferably of from 10 to 20 % by weight of the one or more anionic surfactants.

In a further preferred embodiment of the invention the inventive laundry detergent compositions are free of phosphate and zeolite compounds.

Optional Ingredients

The inventive laundry detergent compositions may or may not comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in laundry detergent compositions. Examples of optional ingredients include, but are not limited to builders, further surfactants, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, color protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotopes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for laundry detergent compositions. Such ingredients are not necessarily present but often help the acceptance of the formulation by the customers.

Builders Builders are commonly added to laundry detergent formulations to complex with alkaline earth metal ions (mainly Ca²⁺ and Mg²⁺) from the washing liquor. Such ions can precipitate with anionic surfactants present in the laundry detergent composition, compromising the cleaning performance. The builder system also helps keeping the washing liquor alkaline, enhancing the washing and anti- redeposition effectiveness: at high pH, both fabric and soil become more negative, increasing mutual repulsion.

The laundry detergent compositions of the present invention preferably comprise, based on the total weight of the inventive laundry detergent compositions, of from 1 to 80 % by weight, more preferably of from 1 to 50 % by weight and even more preferably of from 15 to 50 % by weight of a builder system, i.e. of one or more builders.

The builders optionally used in the inventive laundry detergent compositions are different from phosphate and zeolite compounds.

Suitable builder compounds include, but are not limited to, alkali metal carbonates, bicarbonates, borates, silicates, layered silicates, polycarboxylic acids, such as lactic acid, glycolic acid, succinic acid, maleic acid, tartaric acid fumaric acid, citric acid or their salts, polycarboxylat.es, homo- and copolymers such as polyacrylates, polyacetates, polyhydroxyacrylates and polyacetates. In a preferred embodiment of the invention the inventive laundry detergent compositions comprise one or more builders selected from the group consisting of silicates, layered silicates, carbonates, polycarboxylates, citrates, bicarbonates and mixtures thereof, and more preferably in an amount, based on the total weight of the inventive laundry detergent compositions, of from 1 to 80 % by weight, preferably of from 1 to 50 % by weight and more preferably of from 15 to 50 % by weight.

Further Surfactants In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 50 % by weight, preferably of from 5 to 30 % by weight and more preferably of from 10 to 20 % by weight of a surfactant system, i.e. of one or more surfactants, different from the one or more cationic surfactant compounds of the formula (1 ) and different from anionic surfactants. This surfactant system different from the one or more cationic surfactant compounds of the formula (1 ) and different from anionic surfactants can comprise a single surfactant or a mixture of surfactants. Non-limiting examples of surfactants different from the one or more cationic surfactant compounds of the formula (1 ) and different from anionic surfactants and useful in the inventive compositions are nonionic, cationic, zwitterionic, amphoteric surfactants and mixtures thereof. Preferred surfactants different from the one or more cationic surfactant compounds of the formula (1 ) and different from anionic surfactants and useful in the inventive compositions are nonionic surfactants and in particular the nonionic surfactants further described below.

For the purpose of this invention, nonionic surfactants can be used in order to reduce the sensibility of the formulation to hard water, to control the sudsing or foaming profile and also as a synergistic agent. Suitable nonionic surfactants for use in the inventive compositions comprise any conventional nonionic surfactant commonly used in laundry detergent compositions. Preferred nonionic surfactants are fatty alcohol ethoxylates of the formula RO(EO)_nH

wherein R is a linear or branched alkyl chain of from 4 to 30 carbon atoms, preferably of from 10 - 18 carbon atoms (EO) is CH₂CH₂O and n is an average number of from 0.5 to 20 and preferably of from 3 to 10.

Other nonionic surfactants that may also be used in the inventive laundry • detergent compositions are alkyl phenol ethoxylates, condensates of alkanolamines with fatty acids such as cocamide diethanolamine (cocamide DEA), polyol-fatty acid esters, ethoxylated polyol-fatty acid esters, alkylpolyglucosides.

Additional nonionic surfactants not specifically mentioned above may also be used in the inventive laundry detergent compositions.

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 50 % by weight, preferably of from 5 to 30 % by weight and more preferably of from 10 to 20 % by weight of one or more surfactants different from the one or more cationic surfactant compounds of formula (1 ) and different from anionic surfactants and selected from the group consisting of nonionic, cationic, zwitterionic, amphoteric surfactants and mixtures thereof.

In a particularly preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions,

e) of from 1 to 80 % by weight, preferably of from 1 to 50 % by weight and more preferably of from 15 to 50 % by weight of one or more builders different from phosphate and zeolite compounds, and f) of from 0.01 to 50 % by weight, preferably of from 5 to 30 % by weight and more preferably of from 10 to 20 % by weight of one or more surfactants different from the one or more cationic surfactant compounds of formula (1 ) and different from anionic surfactants and selected from the group consisting of nonionic, cationic, zwitterionic, amphoteric surfactants and mixtures thereof.

Bleaching Agents

Bleaching agents are commonly used in laundry detergent compositions to remove hydrophilic soils, generally derived from vegetables and containing polyphenols compounds, by oxidative decomposition of chromophoric systems. The bleach system of laundry detergent compositions may comprise a bleach active compound, a bleach activator, a bleach catalyst, such as a photobleach, and mixtures thereof. The compositions of the present invention may preferably comprise, based on the total weight of the inventive laundry detergent compositions, of from 0 to 20 % by weight, more preferably of from 0.5 to 20 % by weight and even more preferably of from 1.5 to 10 % by weight of a bleach system.

Non-limiting examples of bleach-active compounds that may be used in the inventive compositions are inorganic peroxides, inorganic peroxohydrates, organic peroxy acids and their salts, chlorine based bleaches and mixtures thereof. Preferred bleach-active compounds are sodium perborate mono- or tetrahydrate and sodium percarbonate,

Non-limiting examples of bleach activators are tetraacetylglycoluril (TUG), tetraacetylethylenediamine (TAED), sodium p-isononanoyloxybenzenesulfonate (iso-NOBS), pentaacetyl glucose (PAG), nitrile quats, benzoxazin derivatives, acyl lactam derivatives, morpholines and mixtures thereof.

Non-limiting examples of bleach catalysts suitable for the present invention are metal chelate bleach catalysts based on manganese, iron, cobalt, titanium, molybdenium, nickel, chromium, copper, heavy metals and photobleaches such as aluminum or zinc phtalocyaninetetrasulfonate and mixtures thereof and preferably heavy metal chelates and photobleaches such as aluminum or zinc phthalocyaninetetrasulfonate and mixtures thereof.

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0 to 20 % by weight, preferably of from 0.5 to 20 % by weight and even more preferably of from 1.5 to 10 % by weight, of one or more bleaching agents selected from the group consisting of

hi ) one or more bleach-active compounds selected from the group consisting of inorganic peroxides, inorganic peroxohydrates, organic peroxy acids and their salts, chlorine based bleaches and mixtures thereof;

h2) one or more bleach activators selected from the group consisting of tetraacetylglycoluril (TUG), tetraacetylethylenediamine (TAED), sodium p-isononanoyloxybenzenesulfonate (iso-NOBS), pentaacetyl glucose (PAG), nitrile quats, benzoxazin derivatives, acyl lactam derivatives, morpholines and mixtures thereof;

h3) one or more bleach catalysts selected from the group consisting of heavy metal chelates and photobleaches such as aluminum or zinc phtalocyaninetetrasulfonate and mixtures thereof;

and mixtures thereof.

Dye Transfer Inhibition Agents (DTI Agents) and Color Care Agents Dye transfer inhibitors (DTI) are commonly used in laundry detergent compositions to prevent dye transfer from one cloth to another one during the washing cycle. The compositions of the present invention may preferably comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 10 % by weight and more preferably of from 0.05 to 0.5 % by weight of one or more dye transfer inhibiting agents. The laundry detergent compositions of the present invention may comprise one or more dye transfer inhibition agents known in the art. Non-limiting examples of DTI agents are homo- and copolymers of N-vinylpirrolidone, N-vinylimidazole and 4-vinylpyridine-N-oxide, reaction products of polyamines with cyanamides and organic and/or inorganic acids or cyanamides with aldehydes and ammonium salts or cyanamides with aldehydes and amines or amines with epichlorohydrin, polyamines and polyamine derivatives, polyimines and polyimine derivatives, cationic polyelectrolytes, polymers containing imidazoline units, bischloromethylbiphenyl polyquats and mixtures thereof. Other non-limiting examples of DTI agents that may be used in the inventive compositions are those described in DE 101 50 723 A1 , WO 97/42291 , EP 1 805 290 A1 and WO 2006/045482 A1.

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 10 % by weight and preferably of from 0.05 to 0.5 % by weight of one or more dye transfer inhibitors and/or color care agents selected from the group consisting of homo- and copolymers of N-vinylpirrolidone, N-vinylimidazole and 4-vinylpyridine-N-oxide, reaction products of polyamines with cyanamides and organic and/or inorganic acids or cyanamides with aldehydes and ammonium salts or cyanamides with aldehydes and amines or amines with epichlorohydrin, polyamines and polyamine derivatives, polyimines and polyimine derivatives, cationic polyelectrolytes, polymers containing imidazoline units, bischloromethylbiphenyl polyquats and mixtures thereof.

Anti-Redeposition and Dispersing Agents

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 10 % by weight of one or more anti- redeposition and/or dispersing agents selected from the group consisting of carboxymethylcellulose, vinylpyrrolidone-based polymers, homo- and copolymers of carboxylates, such as acrylic and maleic acid homo- and copolymers, and mixtures thereof. Fabric Softeners and Anti-Static Agents

Softeners/anti-static agents may optionally be added to the laundry detergent compositions of the present invention. Non-limiting examples of softening/antistatic agents that may be used in the inventive compositions are inorganic clays, such as bentonites, illites, attapulgites, kaolinites, montmorillonites, saponites, hectorites, quaternary ammonium compounds, mainly di-long alkyl chain ammoniun compounds such as ditallow dimethylammonium chloride, dihydrogenated tallow dimethylammonium chloride or methylsulfate, distearyl dimethylammonium chloride, alkyl or aryl amines, fatty acids, phosphate esters, silicones and mixtures thereof. Other non-limiting examples of fabric softeners and anti-static agents that may be used in the inventive compositions are those described in US 4,291 ,071 , US 4,375,416, US 4,062,647 and US 7,012,054.

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 10 % by weight of one or more fabric care, fabric conditioning or antistatic agents selected from the group consisting of mineral clays, such as smectite and kaolinite, cationic and polycationic compounds, silicone oils, amines, polyamines, fatty acids, phosphate esters and mixtures thereof.

Fluorescent Whitening Agent (Optical Brightener)

Any optical brightener or brightening or whitening agents known in the art may be used in the inventive compositions. Preferred amounts of such agents are of from 0.0001 to 5 % by weight, preferably of from 0.01 to 1 % by weight and even more preferably of from 0.03 to 0.5 % by weight, based on the total weight of the inventive laundry detergent compositions. Non-limiting examples of suitable brightening or whitening agents are 4,4'-Bis (triazinylamino) stilbene-2,2'- disulfonic acids, 4,4'-Bis(υ-triazol-2yl)stilibene-2,2'-disulfonic acids, Stilbenylnaphthotriazoles, 4,4'-Bis(styryl) biphenyls, Pyrazolines, Coumarins, Quinolones, Bis(benzoxazol-2-yl) derivatives, Bis(benzimidazol-2-yl) derivatives, 2-Styrylbenzoxazoles and naphthoxazoles and mixtures thereof. In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.0001 to 5 % by weight, preferably of from 0.01 to 1 % by weight and even more preferably of from 0.03 to 0.5 % by weight of one or more fluorescent whitening agents selected from the group consisting of 4,4'-Bis (triazinylamino) stilbene-2,2'-disulfonic acids, 4,4'-Bis(υ-triazol- 2yl)stilibene-2,2'-disulfonic acids, Stilbenylnaphthotriazoles, 4,4'-Bis(styryl) biphenyls, Pyrazolines, Coumarins, Quinolones, Bis(benzoxazol-2-yl) derivatives, Bis(benzimidazol-2-yl) derivatives, 2-Styrylbenzoxazoles and naphthoxazoles and mixtures thereof.

Enzymes

The laundry detergent compositions of the present invention may preferably comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.0001 to 5 % by weight, more preferably of from 0.1 to 1 % by weight and even more preferably of from 0.1 to 0.5 % by weight of an enzymatic system. The enzymes most commonly found in laundry detergent formulations are proteases, lipases, amylases, cellulases and mixtures thereof. However, other types of enzymes, such as lipoxygenases, hemicellulases, peroxidases, mannanases, cutinases, reductases, oxidases, pectinases, ligninases, beta-glucanases, pullulanases, tannases, pentosanases, malanases and mixtures thereof can be included.

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.0001 to 5 % by weight, preferably of from 0.1 to 1 % by weight and even more preferably of from 0.1 to 0.5 % by weight of one or more enzymes selected from the group consisting of proteases, amylases, gluco- amylases, lipases, lipoxygenases, cellulases, hemicellulases, peroxidases, mannanases, cutinases, reductases, oxidases, pectinases, ligninases, beta- glucanases, pullulanases, tannases, pentosanases, malanases and mixtures thereof. Foam Regulators

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 0.01 to 5 % by weight of one or more foam regulators selected from the group consisting of soaps, nonpolar oils such as mineral and silicone oils, polar oils such as fatty alcohols, fatty acids, alkyl amines, alkyl amides, tributyl phosphate (TBP) and thioethers, hydrophobic organic and inorganic particulates such as silica, AI₂O₃, Tiθ₂, wax, such as magnesium stearate, polymeric particles such as polyamides and polypropylene and mixtures thereof.

In a further preferred embodiment of the invention the inventive laundry detergent compositions comprise one or more substances selected from fragrances, processing aids, dyes and/or pigments, anti-corrosion agents, fillers, stabilizers and other conventional detergent ingredients.

In the context of the present invention the term "solid" means solid at a temperature of 25 ⁰C and at a pressure of 1 atm (1013.25 mbar = 101325 Pa).

Preferably the inventive laundry detergent compositions are present in the form of a powder, granules or tablets and particularly preferably the inventive laundry detergent compositions are present in the form of a powder or granules.

In a preferred embodiment of the invention the inventive laundry detergent compositions comprise, based on the total weight of the inventive laundry detergent compositions, of from 5 to 75 % by weight, preferably of from 20 to 70 % by weight and particularly preferably of from 50 to 68 % by weight of one or more fillers. Preferred fillers are sodium sulphate and sodium chloride.

Additional optional ingredients commonly used in laundry detergent compositions that are not specifically mentioned above may also be used in the inventive compositions. Examples

To better illustrate the embodiments of the present invention, non-limiting examples are given in Table 1.

Table 1 Compositions of Formulation A (invention) and of the Reference

The alkyl dimethyl hydroxyethyl quat used in Formulation A is C₁₂-C₁₄ dimethyl hydroxyethyl quat which is commercially available from Clariant under the trade name Praepagen^® HY.

The nonionic soil release polymer used in Formulation A is a nonionic polyethylene terephthalate and polyoxyethylene terephthalate based polymer (PET-POET polymer) which is commercially available from Clariant under the trade name TexCare^® SRN 400.

Primary Detergency Data

The primary detergency was assessed by a washing test on domestic washing machines. Every formulation was tested in triplicate on a set of 3 soils on 2 different substrates, as described in Tables 2, 3a and 3b. The primary detergency is evaluated visually and colorimetrically. The colorimetric evaluation is made by calculating the color difference (DE CMC according to ASTM D2244) between each test swatch after and before washing. The higher the DE CMC, the better the primary detergency. The average color difference is calculated for each soil and the means are compared.

For the visual evaluation, the swatches washed with each formulation are grouped into tiles and presented to 12 untrained panelists. The panelists analyze the tiles under the same conditions (light, background, distance from the swatches, temperature) and are asked to choose the cleanest set of swatches (preference test). This procedure is made for each different soil and the results given by a score with the number of evaluators that chose each formulation as the best.

Table 2 Primary Detergency Test Conditions

Table 3a Fresh Soils

CO: cotton, PES: polyester Table 3b Standard Soil

CO: cotton, PES: polyester, WFK 10D: cotton soiled with pigment/sebum, WFK 2OD: polyester/cotton soiled with pigment/sebum

WFK 10D and WFK 2OD are commercially available from WFK Testgewebe GmbH.

Table 4 shows the sum of the color differences of all of the tested soils for each formulation. Table 5 shows the results (both colorimetric and visual) for cotton soiled with a mixture of carbon black and olive oil.

The results show a statistically significant benefit of Formulation A (according to the invention). According to the visual panel result (Table 5) 12 out of 12 evaluators have chosen Formulation A as more efficient regarding primary detergency.

Table 4 Primary detergency data; Global Colorimetric Evaluation (Sum of the color differences of all of the tested soils)

Table 5 Primary detergency data for cotton soiled with carbon black - olive oil

Claims

1. Laundry detergent composition present in a solid form and comprising a) one or more cationic surfactant compounds of formula (1 )

R¹

R2 _ N^Φ — R3 X⁰ (1)

I

R⁴

wherein

R¹ is C₈-C₂₂-alkyl, preferably C₈-Ci₄-alkyl and even more preferably C₈-Cio-alkyl or Ci₂-Ci₄-alkyl

R² and R³ are -CH₃ groups

R⁴ is CH₂CH₂OH and

and

c) one or more anionic surfactants,

characterized in that the laundry detergent composition is free of phosphate and zeolite builders.

2. Laundry detergent composition according to claim 1 , characterized in that the one or more soil release polymers of component b) are non-ionic or anionic homo- or copolymers of polyethyleneterephtalate (PET) and/or polyoxyethyleneterephtalate (POET).

3. Laundry detergent composition according to claim 1 or 2, characterized in that it comprises the one or more cationic surfactant compounds of formula (1 ) and the one or more soil release polymers of component b) in a total amount of from 0.001 to 50 % by weight and that the weight ratio of the one or more cationic surfactant compounds of formula (1 ) to the one or more soil release polymers of component b) is of from 50:1 to 1 :50.

4. Laundry detergent composition according to one or more of claims 1 to 3, characterized in that the one or more anionic surfactants according to component c) of the inventive compositions are selected from the group of surfactants consisting of Alkyl Aryl Sulfonates, Alkyl Sulfonates, Alkyl Sulfates, Alkyl Alkoxylated Sulfates, Sulfo Fatty Acid Esters, Salts of Organic Acids (soaps), Sulphosuccinate esters, fatty acid isethionates and taurides, alkyl succinamates, acyl sarcosinates, phosphoric acid esters and salts, acyl glutamates and ether carboxylates.

5. Laundry detergent composition according to one or more of claims 1 to 4, characterized in that it comprises of from 0.01 to 50 % by weight of the one or more anionic surfactants of component c).

6. Laundry detergent composition according to one or more of claims 1 to 5, characterized in that it is free of phosphate and zeolite compounds.

7. Laundry detergent composition according to one or more of claims 1 to 6, characterized in that it comprises of from 1 to 80 % by weight of one or more builders different from phosphate and zeolite compounds.

8. Laundry detergent composition according to one or more of claims 1 to 7, characterized in that it comprises one or more builders selected from the group consisting of silicates, layered silicates, carbonates, polycarboxylates, citrates, bicarbonates and mixtures thereof.

9. Laundry detergent composition according to one or more of claims 1 to 8, characterized in that it comprises of from 0.01 to 50% by weight of one or more surfactants different from the one or more cationic surfactant compounds of formula (1 ) and different from anionic surfactants and selected from the group consisting of honionic, cationic, zwitterionic, amphoteric surfactants and mixtures thereof.

10. Laundry detergent composition according to one or more of claims 1 to 9, characterized in that it comprises of from 0 to 20 % by weight of one or more bleaching agents selected from the group consisting of

h3) one or more bleach catalysts selected from the group consisting of heavy metal chelates and photobleaches such as aluminum or zinc phtalocyaninetetrasulfonate and mixtures thereof; and mixtures of the substances of components hi ), h2) and/or h3).

11. Laundry detergent composition according to one or more of claims 1 to 10, characterized in that it comprises of from 0.01 to 10 % by weight of one or more dye transfer inhibitors and/or color care agents selected from the group consisting of homo- and copolymers of N-vinylpirrolidone, N-vinylimidazole and 4-vinylpyridine-N-oxide, reaction products of polyamines with cyanamides and organic and/or inorganic acids or cyanamides with aldehydes and ammonium salts or cyanamides with aldehydes and amines or amines with epichlorohydrin, polyamines and polyamine derivatives, polyimines and polyimine derivatives, cationic polyelectrolytes, polymers containing imidazoline units, bischloromethylbiphenyl polyquats and mixtures thereof.

12. Laundry detergent composition according to one or more of claims 1 to 11 , characterized in that it comprises of from 0.01 to 10 % by weight of one or more anti-redeposition and/or dispersing agents selected from the group consisting of carboxymethylcellulose, vinylpyrrolidone-based polymers, homo- and copolymers of carboxylates, such as acrylic and maleic acid homo- and copolymers, and mixtures thereof.

13. Laundry detergent composition according to one or more of claims 1 to 12, characterized in that it comprises of from 0.01 to 10 % by weight of one or more fabric care, fabric conditioning or antistatic agents selected from the group consisting of mineral clays, such as smectite and kaolinite, cationic and polycationic compounds, silicone oils, amines, polyamines, fatty acids, phosphate esters and mixtures thereof.

14. Laundry detergent composition according to one or more of claims 1 to 13, characterized in that it comprises of from 0.0001 to 5 % by weight of one or more fluorescent whitening agents selected from the group consisting of 4,4'-Bis (triazinylamino) stilbene-2,2'-disulfonic acids, 4,4'-Bis(υ-triazol-2yl)stilibene-2,2'- disulfonic acids, Stilbenylnaphthotriazoles, 4,4'-Bis(styryl) biphenyls, Pyrazolines, Coumarins, Quinolones, Bis(benzoxazol-2-yl) derivatives, Bis(benzimidazol-2-yl) derivatives, 2-Styrylbenzoxazoles and naphthoxazoles and mixtures thereof.

15. Laundry detergent composition according to one or more of claims 1 to 14, characterized in that it comprises of from 0.0001 to 5 % by weight of one or more enzymes selected from the group consisting of proteases, amylases, gluco- amylases, lipases, lipoxygenases, cellulases, hemicellulases, peroxidases, mannanases, cutinases, reductases, oxidases, pectinases, ligninases, beta- glucanases, pullulanases, tannases, pentosanases, malanases and mixtures thereof.

16. Laundry detergent composition according to one or more of claims 1 to 15, characterized in that it comprises of from 0.01 to 5 % by weight of one or more foam regulators selected from the group consisting of soaps, nonpolar oils such as mineral and silicone oils, polar oils such as fatty alcohols, fatty acids, alkyl amines, alkyl amides, tributyl phosphate (TBP) and thioethers, hydrophobic organic and inorganic particulates such as silica, AI₂O₃, TΪO₂, wax, such as magnesium stearate, polymeric particles such as polyamides and polypropylene and mixtures thereof.

17. Laundry detergent composition according to one or more of claims 1 to 16, characterized in that it comprises one or more substances selected from the group consisting of fragrances, processing aids, dyes and/or pigments, anti-corrosion agents, fillers, stabilizers and other conventional detergent ingredients.

18. Laundry detergent composition according to one or more of claims 1 to 17, characterized in that it is present in the form of a powder, granules or tablets.

19. Laundry detergent composition according to one or more of claims 1 to 18, characterized in that it comprises of from 5 to 75 % by weight of one or more fillers, preferably sodium sulphate and/or sodium chloride.