ES2421162T3 - Fabric washing procedure - Google Patents

Abstract

A process for washing fabrics on which a cationic fabric-softening active substance has been deposited and dried, comprising the step of contacting the fabric with an aqueous washing liquor which has the following composition: a) 15 to 600 ppm surfactant non-soapy, b) at least 50 ppm of ethoxylated polyethyleneimine, c) at least 25 ppm of polyester dirt-release polymer, the total polymer level (b + c) being at least 20% by weight of the level of the non-soap surfactant (a), d) 0.1 to 100 ppm of the enzyme selected from protease, amylase, cellulase, and e) optionally, the enzyme lipase.

Description

Fabric washing procedure

Technical field

The present invention relates to a process of washing textile material on which a quaternary ammonium fabric softener compound has been deposited and dried.

Background

It is known that cationic rinse conditioners are almost completely depleted on fabrics during the washing procedure. For example, from "Liquid Detergents", published in 2006, CRC press page 490, it is known that anionic surfactants will form complexes with cationic assets and that the resulting complex can be deposited on fabrics and, as a result, can be seen reduced stain removal performance of detergent products comprising anionic surfactants. At lower levels of surfactants during washing, this loss of performance can be expected to become more significant. This forecast is supported by the teaching in WO93 / 018124 (P&G) which, although it mainly refers to granular detergent compositions, one would expect to also apply it to liquids because the effect occurs during washing. This document indicates that there is interest in the development of detergent compositions that include a surfactant system comprising only low levels of the anionic surfactant. According to WO93 / 018124, a disadvantage of formulating said compositions is that the detergency performance can be altered by the high degree of complexation of the low level of anionic surfactants by the cationic fabric softening components that may be present in The wash solution. Said cationic fabric softener components can be introduced into the wash solution as residues on the fabrics to be washed due to the pretreatment of the fabric with a fabric conditioning composition containing said cationic softening components.

WO93 / 018124 claims a detergent composition comprising low levels (5% to 10% combined weight) of a combination of water-soluble alkyl ethoxysulfate anionic surfactant and alkyl sulfate anionic surfactant in combination at specific weight ratios. Although this document discloses "solid detergency yield" of the composition even in the presence of cationic fabric softening components in the wash solution, the examples use a cationic fabric conditioner based on imidazoline and show less yellowing (loss of whiteness) more than a better removal of dirt (stains). It is well documented that imidazoline active substances have yellowing problems (see, Levinson. J. Surfactants and Detergents vol 2 (2) 223-235 (see table 4 p. 230)). The solution to this problem through the use of alkyl sulfates is known from US 3 644 203, which teaches that the anti-yellowing effect is due to the formation of alkyl sulfate complexes with the cationic fabric softener in the composition (in the presence of other ingredients). The development in WO93 / 018124 appears to be to form the anti-yellowing complex through the use of the anionic alkyl sulfate or alkyl ether sulfate surfactant drawn from the main wash to the rinse.

WO2009 / 153184 describes a method of washing fabrics using very low levels of surfactant during washing, preferably comprising anionic surfactant. The washing performance is reinforced by the inclusion of high levels of specific polymers and enzymes. The expert would expect that compositions that release such low levels during the washing of anionic surfactant would be more affected by the cationic drag on the previous wash / rinse fabric than the compositions and washing procedures that release higher levels of anionic surfactant. during washing.

Surprisingly, the inventors have discovered that when the compositions and the process described in WO2009 / 153184 are used, a much smaller reduction in yield occurs during washing on the fabric treated with cationic rinse conditioner than the effect observed for liquids prior art detergents, even those containing the soluble alkyl ethoxy sulfate claimed to improve detergency in WO93 / 018124 ..

It is taught in the art to formulate some washing detergents with mixtures of anionic and cationic surfactants (usually less of the latter). Typically, the cationic is used to modify the packaging behavior of the surfactant system to make it more lamellar. The cationic active substances of the rinse conditioner, including the imidazoline active substances, normally have two long alkyl chains and these do not exhibit the same benefits of the composition as cationic surfactants with a fatty alkyl chain (usually shorter).

Consumers use fabric conditioners a lot. It would be advantageous to identify a washing composition that could be used in a washing detergent process so that the washing performance is less compromised by the prior use of a fabric conditioner.

Summary of the invention

In accordance with the present invention there is provided a method of washing fabrics on which a cationic fabric softener active substance has been deposited and dried, the step comprising contacting the fabric with an aqueous washing liquor having the composition next:

a) 15 to 600 ppm of non-soap surfactant,

b) at least 50 ppm of ethoxylated polyethyleneimine,

c) at least 25 ppm of polyester dirt release polymer,

the total polymer level (b + c) being at least 20% by weight of the level of the non-soap surfactant (a),

d) 0.1 to 100 ppm of the enzyme selected from protease, amylase, cellulase,

e) optionally, the enzyme lipase.

Preferably, the level of the non-soap surfactant (a) is from 200 to 400 ppm. Typically, the non-soap surfactant (a) comprises at least 50 ppm of anionic surfactant.

Advantageously, the EPEI is non-ionic. The cationic fabric softener active substance is preferably a quaternary ammonium compound.

The polyester dirt release polymer (c) is preferably non-ionic and, more preferably, comprises in the middle a substantive polyester block of terephthalate repeat units and one or more polyethylene glycol terminal blocks with a lower alkyl or a Hydrogen residue at its end.

The wash liquor can be formed by adding to the water doses of 15 to 40 ml of an aqueous liquid detergent composition and diluting by a factor of at least 600.

More preferably, the non-soap surfactant comprises linear alkyl benzenesulfonate (LAS), sodium lauryl ether sulfate (SLES) and non-ionic ethoxylated fatty alcohol, even more preferably the non-soap surfactant further comprises carbobetaine.

The surfactant-poor composition used in this process may still suffer a reduction in detergency performance on some stains when the load to be washed has previously been exposed to a wash conditioner. Surprisingly, however, this reduction is much smaller with respect to the losses observed for prior art detergent liquids used at their recommended doses. This is surprising because it was expected that higher detergent levels would lead to a smaller effect and the decrease in detergent levels during washing, in particular anionic detergent levels would increase any problem caused by the dragging of the cationic rinse conditioner.

Detailed description of the invention

To form the wash liquor for use in the process according to the invention a concentrated wash liquid with lower than expected levels of the surfactant is used as described in WO2009 / 153184. Therefore, in one embodiment a dose of a low volume, less than 25 ml and, preferably, approximately 20 ml of the concentrated liquid is introduced into a wash load and diluted with water to form the wash liquor for use in the process. Although the exact dilution will vary from one load to another and from one washing machine to another, it is expected that compositions suitable for use in the process according to the invention may comprise the ingredients described below at the levels detailed below.

Detergent liquids

Compositions for use in the process of the invention comprise detersory surfactant. The non-soapy detersory surfactant represents at least 10% by weight of the liquid composition, preferably represents 12 to 60% by weight. The compositions for use according to the invention have, more preferably, total levels of active detersory surfactant of at least 15% by weight.

In the process, the compositions are used in small doses that have to be diluted in at least 500 times their own volume of water to form a main wash liquor comprising, at most, 0.5 g / l of surfactant. They can be concentrated compositions designed for automatic front-loading washing machines, for hand washing or for automatic top-loading washing machines. Less water can be used in handwashing and in higher-load automatic washing machines, a higher amount of water would normally be used than in automatic front-loading washing machines. The dose of liquid detergent is adjusted accordingly to give similar concentrations of the wash liquor.

Surfactants

Surfactants help remove dirt from textile materials and also help keep dirt removed in solution or suspension in the wash liquor. A preferred feature of the present invention is anionic surfactants, or mixtures of anionic and nonionic surfactants. The amount of anionic surfactant is preferably at least 5% by weight. Preferably, the anionic surfactants form the majority of the non-soap surfactants (a).

Anionic surfactants

Preferred alkyl sulfonates are alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) having a length of the C8-C15 alkyl chain. Generally, the counterion for anionic surfactants is an alkali metal, usually sodium, although other counterions such as MEA, TEA or ammonium can be used. Suitable anionic surfactants are available on the market such as the Clariant Genapol series. Preferred linear alkylbenzene sulphonate surfactants are Retail LAS with an alkyl chain length of 8 to 15, more preferably 12 to 14.

It is desirable that the composition further comprises an anionic alkyl polyethoxylate sulfate surfactant of the formula (I):

-

M +

RO (C2H4O) xSO3 (I)

wherein R is an alkyl chain having 10 to 22 carbon atoms, saturated or unsaturated, M is a cation that forms the water-soluble compound, especially an alkali metal, ammonium or substituted ammonium cation, and x is the average of 1 to 15.

Preferably, R is an alkyl chain having 12 to 16 carbon atoms, M is sodium and x is the average of 1 to 3, preferably x is 3; This is the lauryl ester sulfate anionic surfactant (SLES). It is the sodium salt of lauryl ether sulfonic acid in which the predominantly C12 lauryl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.

Although less preferred, some alkyl sulfate surfactant (PAS) can be used, especially the non-ethoxylated C12-15 alkyl sulfates. A particularly preferred material, commercially available from Cognis, is Sulphopon 1214G.

Preferably, the PAS is used mixed with LAS and, more preferably, mixed with LAS and SLES. A preferred SLES / AO / LAS / PAS liquid has a detersory surfactant system comprising 60 parts of SLES, 20 parts of amine oxide, 10 parts of LAS and 10 parts of PAS.

Nonionic Surfactants

Nonionic surfactants include primary and secondary alcohol ethoxylates, especially ethoxylated C8-C20 aliphatic alcohol with an average of 1 to 20 moles of ethylene oxide per mole of alcohol and, more especially, primary and secondary aliphatic C10-C20 alcohols. ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide). Mixtures of non-ionic surfactant can be used. When included, the composition contains from 0.2% by weight to 40% by weight, preferably from 1% by weight to 20% by weight, more preferably from 5 to 15% by weight of a non-ionic surfactant, such as ethoxylate of alcohol, nonylphenol ethoxylate, alkyl polyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxyalkyl fatty acid amide or N-acyl derivatives N-alkyl glucosamine ("glucamides").

Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, especially ethoxylated C8-C20 aliphatic alcohols with an average of 1 to 35 moles of ethylene oxide per mole of alcohol and, more especially, primary and aliphatic alcohols. of C10-C15 ethoxylates with an average of 1 to 10 moles of ethylene oxide per mole of alcohol.

Amine Oxide Surfactants

The composition may comprise up to 10% by weight of an amine oxide of the formula (2):

R1N (O) (CH2R2) 2 (2)

Where R1 is a long chain residue and each CH2R2 is a short chain residue. R2 is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl moiety that can be saturated or unsaturated, preferably, R1 is a primary alkyl moiety. R1 is a hydrocarbyl moiety having a chain length of about 8 to about 18.

In the preferred amide oxides, R1 is C8-C18 alkyl and R2 is H. These amine oxides are illustrated by C12-14 alkyldimethylamine oxide, hexadecyldimethylamine oxide, octadecylamine oxide.

A preferred amine oxide material is lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Said amine oxide material is commercially available from Hunstman under the Empigen® OB brand.

Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See the McCutcheon compilation and the Kirk-Othmer review article for alternative manufacturers of amine oxide.

While in some of the preferred embodiments R2 is H, it is possible that R2 is a larger moiety than H. Specifically, R2 may be CH2OH, such as: hexadecylbis (2-hydroxyethyl) amine oxide, tallowbis (2-hydroxyethyl) oxide amine, stearylbis (2-hydroxyethyl) amine oxide and oleylbis (2-hydroxyethyl) amine oxide.

Preferred amine oxides have the formula (3):

O - N + (Me) 2R1 (3)

wherein R1 is C12-16 alkyl, preferably C12-14 alkyl; Me is a methyl group.

Zwitterionic Surfactants

Non-ionic systems with up to 95% by weight of LAS can be manufactured whenever a zwitterionic surfactant, such as sulfobetaine, is present. A preferred zwitterionic material is a betaine available from Hunstman under the Empigen® BB brand. Betaines improve the detergency of particulate dirt in the compositions of the invention.

Cationic surfactants

Preferably, cationic surfactants are substantially absent.

Soap

The compositions may comprise soap that can act as an additive and / or as a defoamer. The amount of non-soap anionic surfactant must exceed the amount of soap. The amount of soap must be less than or equal to 15% by weight of the total liquid composition.

Polymers

EPEI

The composition comprises an ethoxylated polyethyleneimine (EPEI) polymer for cleaning. Preferably, the EPEI is non-ionic. This means that it has no quaternary nitrogen or nitrogen oxides or any ionic species apart from the possible protonation of the nitrogen affected by the pH.

Polyethyleneimines (PEI, especially modified PEI) are materials composed of ethyleneimine units, -CH2CH2NH, and, when branched, hydrogen on nitrogen is replaced by another chain of ethyleneimine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. In US Pat. No. 2,182,306, Ulrich et al., Filed December 5, 1939; U.S. Patent No. 3,033,746, Mayle et al., Filed May 8, 1962; U.S. Patent No. 2,208,095, Esselmann et al., Filed July 16, 1940; U.S. Patent No. 2,806,839, Crowther, filed September 17, 1957; U.S. Patent No. 2,553,696, Wilson, filed May 21, 1951 and WO2006 / 086492 (BASF) disclose specific procedures for preparing these polyamine structures.

Preferably, the EPEI comprises a polyethyleneimine structure in which the modification of the polyethyleneimine structure is to leave the polymer un quaternized. Said non-ionic EPEI can be represented as PEI (X) YEO, wherein X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine structure. The ethoxylation number Y may vary from 9 to 40 epoxy moieties by modification, preferably it is in the range of 16 to 26, more preferably from 18 to 22. X is selected from about 300 to about 10,000 weight average molecular weight and is, preferably, about 600.

The ethoxylated polyethyleneimine (EPEI) polymer is present in the composition at a level of, preferably, between 0.01 and 25% by weight, but more preferably at a level of at least 2% by weight and / or less from 9.5% by weight, more preferably from 3 to 9% by weight, and with a proportion of non-soap surfactant and EPEI from 2: 1 to 7: 1, preferably from 3: 1 to 6: 1, or even to 5: 1.

Dirt-releasing polymer

The composition comprises at least 0.5% by weight of a soil-releasing polymer for the removal of

oily dirt, especially polyester.

Dirt-releasing polymers improve the performance of the main wash of the compositions when used in the process with low surfactant levels during the washing of the present invention.

A preferred class of polymer is that of the substantive polymers of fabrics comprising at least one of (i) saccharide or (ii) dicarboxylic acid and monomeric units of polyol. Normally, these have dirt-releasing properties and although they can have a primary detergent effect they generally help in subsequent cleaning. Preferably, these should be present at a level of at least 2% by weight, preferably at least 3% by weight of the composition.

Generally, the soil-release polymer will comprise up to 10% by weight of the detergent composition, preferably from 3% by weight to 95 by weight, but more preferably they are used at more than 2% by weight and, more preferably, more than 3% by weight, even more preferably more than 5% by weight, that is 6 to 8% by weight in the composition.

Generally, the soil-releasing polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).

The polymeric dirt-release agents useful herein include, especially, the dirt-releasing agents that have:

(to)

 one or more non-ionic hydrophilic components consisting essentially of:

(i)

 polyoxyethylene segments with a degree of polymerization of at least 2, or

(ii)

 segments of oxypropylene or polyoxypropylene with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not cover any unit of oxypropylene unless it is attached to adjacent moieties at each end by ether bonds, or

(iii) a mixture of oxyalkylene units comprising oxyethylene and 1 to about 30 oxypropylene units in which said mixture contains a sufficient amount of oxyethylene units in such a way that the hydrophilic component has a hydrophilicity large enough to increase the hydrophilicity of the synthetic fiber surfaces of the conventional polyester after deposition of the soil release agent on said surface, said hydrophilic segments preferably comprising at least about 25% oxyethylene units and, more preferably, especially for said components, have approximately from 20 to 30 units of oxyethylene, about at least 50% of units of oxyethylene or

(b)

 one or more hydrophobic components comprising:

(i)

segments of C3 oxyalkylene terephthalate, in which if said hydrophobic components also comprise oxyethylene terephthalate, the ratio between oxyethylene terephthalate units: C3 oxyethylene terephthalate is about 2: 1 or less,

(ii)

 C4-C6 alkylene segments or C4-C6 oxyalkylene segments,

(iii) segments of poly (vinyl ester), preferably polyvinyl acetate, having a degree of polymerization of at least 2 or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl substituents, or mixtures thereof, in which said substituents are present in the form of C1-C4 alkyl ether or hydroxyalkyl ether cellulose derivatives, or mixtures thereof, and said cellulose derivatives are amphiphilic, so that they have a sufficient level of C1-C4 alkyl ether units and / or of C4 hydroxyalkyl ether to deposit on conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to said conventional synthetic fiber surface, to increase the hydrophilicity of the fiber surface, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of about 200, although higher levels may be used, preferably from 3 to about 150, more preferably from 6 to about 100. Hydrophobic segments of C4 oxyalkylene -C6 include, among others, terminals of polymeric dirt-release agents, such as MO3 S (CH2) n OCH2 CH2 O--, in which M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent No. 4,721,580, filed on January 26, 1988 by Gosselink.

Dirt-releasing agents characterized by hydrophobic segments of poly (vinyl ether) include poly (vinyl ether) graft copolymers, for example C1-C6 vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide structures, such as polyethylene oxide structures. See European Patent Application 0 219 048, published April 22, 1987, of Kud, et al., Commercially available dirt release agents of this type include the type of SOKALAN material. For example SOKALAN HP-22, available in BASF (West Germany).

A preferred type of soil release agent is a copolymer having randomized blocks of ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See US Pat. No. 3,959,230 to Hays, filed May 25, 1976 and U.S. Pat. 3,893,929 of Basadur filed on July 8, 1975.

Another polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units containing from 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units, derivatives of a polyoxyethylene glycol of average molecular weight 300

5,000 Examples of this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also US Pat. No. 4,702,857 filed October 27, 1987, from Gosselink.

Another polymeric soil-releasing agent is a sulfonated product of a substantially linear ester oligomer composed of an oligomeric ester structure of terephthaloyl and oxyalkyleneoxy repeating units and terminal moieties covalently bonded to the structure. These dirt release agents are fully described in US Pat. No. 4,968,451, filed on November 6, 1990 by J.J. Scheibel and E.

P. Gosselink. Other polymeric soil release agents include terephthalate polyesters of US Pat. No. 4,711,730, filed December 8, 1987 by Gosselink et al., Anionic oligomeric esters with capped ends of US Pat. No. 4,721,580, filed January 26, 1988 by Gosselink, and the oligomeric block polyester compounds of US Pat. No. 4,702,857, filed October 27, 1987 from Gosselink.

Preferred polymeric soil release agents also include the soil release agents of US Pat. No. 4,877,896, filed October 31, 1989, from Maldonado et al, which discloses terephthalate esters with anionic capped ends, especially sulfoarolyl.

Another soil-releasing agent is an oligomer with repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethylene oxides and oxy-1,2-propylene units. The repeat units form the structure of the oligomer and, preferably, are terminated with modified isethionate end protectors. A particularly preferred soil release agent of this type comprises approximately one unit of sulphosiophthaloyl, 5 units of sulfoisophthaloyl, 5 units of terephthaloyl, units of oxyethylene and oxy-1,2-propylene oxide in a proportion of about 1.7 to about 1.8, and two units with plugged ends of sodium 2- (2-hydroxyethoxy) -ethanesulfonate. Said soil release agent also comprises from about 0.5% to about 20% by weight of the oligomer, of a crystalline reducing stabilizer, preferably selected from the group consisting of xylene sulphonate, cumene sulphonate, toluene sulphonate and mixtures thereof.

Suitable soil release polymers are described in WO 2008095626 (Clariant); WO 2006133867 (Clariant); WO 2006133868 (Clariant); WO 2005097959 (Clariant); WO 9858044 (Clariant); WO 2000004120 (Rhodia Chimie); US 6242404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741197 (BASF); EP 728795 (BASF), US 5008032 (BASF); WO 2002077063 (BASF); P 483606 (BASF); EP 442101 (BASF); WO 9820092 (Proctor &Gamble); EP 201124 (Proctor &Gamble); EP 199403 (Proctor &Gamble); DE 2527793 (Proctor &Gamble); WO 9919429 (Proctor &Gamble); WO 9859030 (Proctor &Gamble); US 5834412 (Proctor &Gamble); WO 9742285 (Proctor &Gamble); WO 9703162 (Proctor &Gamble); WO 9502030 (Proctor &Gamble); WO 9502028 (Proctor &Gamble); EP 357280 (Proctor &Gamble); US 4116885 (Proctor &Gamble); WO 9532232 (Henkel); WO 9532232 (Henkel); WO 9616150 (Henkel); WO 9518207 (Henkel); EP 1099748 (Henkel); FR 2619393 (Colgate Palmolive); DE 3411941 (Colgate Palmolive); DE 3410810 (Colgate Palmolive); WO 2002018474 (RWE-DEA MINERALOEL & CHEM AG; SASOL GERMANY GMBH); EP 743358 (Textile Color AG); PL 148326 (Instytut Ciezkiej Syntezy Organicznej "Blachownia", Pol.); JP 2001181692 (Lion Corp); JP 11193397 A (Lion Corp); document RO 114357 (S.C. "Prod Cresus" S.A., Bacau, Rom.); and US 7119056 (Sasol).

Particularly preferable are combinations of relatively high levels of EPEI, in particular higher than 2.5% by weight based on the composition, with dirt-releasing polymers. The inventors have determined that the combination of EPEI and soil-releasing polymers of the above types allows for increased performance at lower surfactant levels compared to 1.0 g / l or higher levels of wash liquors with non-soap surfactants are EPEI nor SRP. This effect is particularly visible in a range of spots on polyester, more particularly red clay. The effect of the combination on sunflower oil and base is also beneficial. SRP performance is significantly enhanced by repeated pretreatment. There is some evidence of a cumulative effect of EPEI performance. The preferred EPEI is nonionic, more preferably it comprises moieties that are not propoxy.

The most preferred soil-releasing polymers are water-soluble / miscible or water dispersible polyesters such as: Linear polyesters marketed as the Rhodia Repel-O-Tex brand (Gerol), or the Clarcare Texcare brand, especially Texcare SRN170, and highly branched polyesters such as those available in Sasol and described in US 7119056. The polyesters are preferably non-ionic and comprise a middle block of separate terephthalate repeat units and at least one terminal block based on polyethylene glycol with a lower alkyl or termination of hydrogen.

Other polymers

In addition to the essential EPEI and polyester dirt-release polymer, the compositions may further comprise pigment transfer inhibition polymers, anti-redeposition polymers and cotton dirt-release polymers, especially those based on modified cellulosic materials.

Enzymes

It is preferable that at least one or more enzymes are present in the compositions for cleaning reinforcement.

Lipase

Lipase is a particularly preferred enzyme. The composition preferably contains from about 5 to about 20,000 UL / g of a lipase. Preferred lipase enzymes include those of bacterial or fungal origin. Protein or chemically modified engineering mutants are included. Examples of useful lipases include Humicola lipases, more preferably those comprising a polypeptide having an amino acid sequence having a sequence identity of at least 90% with the wild lipases derived from Humicola lanuginose, more preferably strain DSM 4109. The amount in the composition is greater than what is normally found in liquid detergents. This can be seen by the proportion between the non-soap surfactant and the enzyme lipase, in particular. A particularly preferred lipase enzyme is available under the Lipoclean ™ brand of Novozymes.

As indicated above, suitable lipases include those of bacterial or fungal origin. Protein or chemically modified engineering mutants are included. Examples of useful lipases include Humicola lipases (synonym Shermomyces), for example of H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or H. insolens as described in WO 96 / 13580, a Pseudomonas lipase, for example P. alkalgenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, for example of B. subtilis (Dartois et al., (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). As indicated above, the preferred ones have a high degree of homology with wild lipase derived from Humicola lanuginose.

Other examples are variants of lipases such as those described in WO 92/05249, WO 94/01541, EP 407 225, EP 260 105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578 , WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202.

Preferred commercially available lipase enzymes include Lipolase ™ and Lipolase Ultra ™, LipeX ™ and Lipoclean ™ (Novozymes A / S).

In addition or as an alternative to lipases, one or more additional enzymes may be present. However, lipase is particularly preferred.

Advantageously, the presence of relatively high levels of calcium in the poorly prepared or unprocessed compositions of the invention has a beneficial effect on the replacement of certain enzymes, in particular lipase enzymes and preferably Humicola lipases.

Preferred lipases include first wash lipases comprising a polypeptide having an amino acid sequence having a sequence identity of at least 90% with the wild lipase derived from the DSM 4109 strain of Humicola lanuginosa and compared with said wild lipases , it comprises a substitution of an electrically neutral or negatively charged amino acid within 15 A of E1 or Q249 with a positively charged amino acid; and you can also understand:

(I)

 a peptide addition at the C terminal;

(II)

 a peptide addition in the N terminal;

(III) the following limitations:

i. it comprises a negatively charged amino acid at position E210 of said wild lipase;

ii. comprises a negatively charged amino acid in the region corresponding to positions 90-101

of said wild lipase; Y

iii. it comprises a neutral or negatively charged amino acid in the N94las position of said wild lipase; I

iv.

it has a negative or neutral charge in the region corresponding to positions 90-101 of said wild lipase; Y

v.

 mixtures thereof.

These are available as the Novozymes Lipex ™ brand. Novozymes has offered a similar Novozymes enzyme but it is believed to be out of the above definition under the name Lipoclean ™, which is also preferable.

Phospholipase:

The process of the invention can be carried out in the presence of phospholipase classified as EC 3.1.1.4 and / or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that has activity against phospholipids. Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in the external (sn-1) and central (sn-2) positions and esterified with phosphoric acid in the third position; Phosphoric acid, in turn, can be esterified with an amino alcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 that hydrolyse a fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid, and lysophospholipase (or phospholipase B) that can hydrolyze the fatty acyl group remaining in lysophospholipid. Phospholipase C and phospholipase D (phosphophiesterases) release diacylglycerol or phosphatidic acid, respectively.

Protease:

Suitable proteases include those of animal, plant or microbial origin. Those of microbial origin are preferred. Protein or chemically modified engineering mutants are included. The protease may be a serine protease or a metalloprotease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase ™, Savinase ™, Primase ™, Duralase ™, Dyrazym ™, Esperase ™, Everlase ™, Polarzyme ™, and Kannase ™, (Novozymes A / S), Maxatase ™, Maxacal ™, Maxapem ™, Properase ™, Purafect ™, Purafect OxP ™, FN2 ™, and FN3 ™ (Genencor International Inc.).

Cutinase:

The process of the invention can be carried out in the presence of cutinase, classified as EC 3.1.1.74. The cutinase used according to the invention can be of any origin. Preferred cutinases are of microbial origin, in particular of bacterial, fungal or yeast origin.

Amylase:

Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Protein or chemically modified engineering mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example a special strain of B. licheniformis, described in more detail in GB 1,296,839, or Bacillus strains disclosed in WO 95/026397 or WO 00 / 060060, Commercially available amylases are Duramyl ™, Termamyl ™, Termamyl Ultra ™, Natalase ™, Stainzyme ™, Fungamyl ™ and BAN ™ (Novozymes A / S), Rapidase ™ and Purastar ™ (from Genencor International Inc.).

Cellulase:

Suitable cellulases include those of bacterial or fungal origin. Protein or chemically modified engineering mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307. Commercially available cellulases include Celluzyme ™, Carezyme ™, Endolase ™, Renozyme ™ (Novozymes A / S), Clazinase ™ and Puradax HA ™ (Genencor International Inc.), and KAC-500 (B) ™ (Kao Corporation).

Peroxidases / oxidases:

Suitable peroxidases / oxidases include those of plant, bacterial or fungal origin. Protein or chemically modified engineering mutants are included. Examples of useful peroxidases include Coprinus peroxidases, for example C. cinereus, and variants thereof such as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include Guardzyme ™ and Novozym ™ 51004 (Novozymes A / S).

Pectato liasas:

Pectate liases (also called polygalacturonate liases): Examples of pectate liases include pectate liases that have been cloned into different bacterial genera such as Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as Bacillus subtilis (Nasser et al. (1993) FEBS Letts. 335: 319-326) and Bacillus sp. YA-14 (Kim et al., (1994) Biosci. Biotech. Biochem. 58: 947-949). The purification of pectate liases with maximum activity in the pH range of 8-10 produced by Bacillus pumilus (Dave and Vaughn (1971) J. Bacteriol. 108: 166-174), B. polymyxa (Nagel and Vaughn (1961) Arch. Biochem. Biophys. 93: 344-352), B. stearothermophilus (Karbassi and Vaughn (1980) Can. J. Microbiol. 26: 377-384), Bacillus sp. (Hasegawa and Nagel (1966) J. Food Sci. 31: 838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24: 1164-1172). Any of the above, as well as pectate divalent liases independent of carions and / or thermosets, can be used in the practice of the invention. In preferred embodiments, the pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976. Pectate liases specifically contemplated are disclosed in WO 99/27083 and WO 99/27084. Other specifically contemplated pectate liases (derived from Bacillus licheniformis) are disclosed in US Pat. No. 6,284,524. Variants of pectate liases specifically contemplated are disclosed in WO 02/006442, specifically the variants disclosed in the examples of WO 02/006442. Examples of commercially available alkaline pectate liases include BIOPREP ™ and SCOURZYME ™ L from Novozymes A / S, Denmark.

Mananasas:

Mannanase: Examples of mananasas (EC 3.2.1.78) include mananasas of bacterial and fungal origin. In a specific embodiment, mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (WO 94/25576). WO 93/24622 discloses an isolated mannanase from Trichoderma reseei. Mananases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol. 56, No. 11, p. 35053510 (1990) describe a beta-mannanase derived from Bacillus stearothermophilus. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, p. 551-555 (1994) describe a beta-mannanase derived from Bacillus subtilis. JP-A-03047076 discloses a beta-mannanase from Bacillus sp. JP-A-63056289 describes the production of an alkaline and thermostable beta-mannanase. JP-A-63036775 refers to the Bacillus FERM P-8856 microorganism that produces beta-mannanase and beta-mannosidase. JP-A08051975 discloses an alkaline beta-mannose alkaline beta-mannanase. AM-001. A purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/11164. WO 91/18974 describes a hemicellulase such as glucanase, xylanase or active manansa. The mananasas of the alkaline family 5 and 26 derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., And Humicola insolens disclosed in WO 99/64619 are contemplated. Especially contemplated are the mananasas of Bacillus sp. Referenced in the Examples in WO 99/64619 Examples of commercially available mananasas include Mannaway ™, available from Novozymes A / S Denmark.

The enzyme and any perfume / fragrance or pro-fragrance present may show some interaction and should be chosen in such a way that this interaction is not negative. Some negative interactions can be avoided by encapsulating one or another enzyme and pro-fragrance and / or other segregation within the product.

Enzymatic stabilizers

Any enzyme present in the composition can be stabilized using conventional stabilizing agents, for example a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative, for example an aromatic borate ester or a phenylboronic acid derivative such as 4-formiulfenylboronic acid, and the composition can be formulated as described in WO 92/19709 and WO 92/19708.

Other optional ingredients

The compositions of the invention may contain one or more additional ingredients. Such ingredients include viscosity modifiers, foam reinforcing agents, preservatives (e.g., bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents , agents that impart fall, antistatic agents and ironing assistants. The compositions may further comprise colorants, pearl and / or opacifying agents, and shading pigments.

Fluorescent agents

It may be advantageous to include fluorescence in the compositions. Normally, these fluorescence agents are supplied and used in the form of their alkali metal salts, for example sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally 0.005 to 2% by weight, more preferably 0.01 to 0.5% by weight.

Preferred classes of fluorescent agents are: Di-styryl biphenyl compounds, for example Tinopal (Trade Mark) CBS-X, composed of di-sulfonic di-amine stilbene di-amine acid, for example Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH , and pyrazoline compounds, for example Blankophor SN.

Preferred fluorescence agents are: 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] triazole sodium, 4,4'-bis {[(4-anilino-6 (N methyl-N- 2 hydroxyethyl) amino 1,3,5-triazin-2-yl)] amino} stilben-2-2 'disodium disulfonate, 4,4'-bis {[(4-anilino-6morpholino-1,3,5-triazin -2-yl)] amino} stilben-2-2 'disulfonate disodium and 4,4'-bis (2-sulfosyryl) biphenyl disodium.

Bleaching catalysts

The detergent compositions according to the invention may comprise a weight efficient bleaching system. Such systems do not normally use the conventional activating approach with percarbonate or perished and / or bleach.

The present invention can be used in a formulation that is used for bleaching with air or an air bleaching catalyst system. Suitable complexes and organic molecule precursors (ligand) to form complexes are available to the skilled worker in, for example: WO 98/39098; WO 98/39406, WO 97/48787, WO 00/29537; WO 00/52124, and WO00 / 6004. An example of a preferred catalyst is a transition emtal complex of the MeN4Py ligand (N, N-bis (pyridin-2-yl-methyl) -1-, 1-bis (pyridin-2i) -1-aminoethane). Suitable bispidon catalyst materials and their action are described in WO02 / 48301.

Photoblanking agents can also be used. In the context of the present invention, a "photobleach" is any chemical species that forms a reactive bleaching species with exposure to sunlight and, preferably, is not permanently consumed in the reaction. Preferred photo bleaches include singlet oxygen photo bleaches and radical photo bleaches. Suitable singlet oxygen photo bleaches can be selected from water-soluble phthalocyanine compounds, in particular metallated phthalocyanine compounds in which the metal is Zn or Al-Z1, where Z1 is a halide, sulfate, nitrate, carboxylate, alkanolate or hydroxyl ion . Preferably, the phthalocyanine has 1-4 SO3X groups covalently bonded thereto, in which X is an alkali metal or ammonium ion. Such compounds are described in WO2005 / 014769 (Ciba).

When present, the bleach catalyst is normally incorporated at a level of about 0.0001 to about 10% by weight, preferably about 0.001 to 5% by weight.

Fragrance

Since the composition of the present invention is designed to be used at very low dose levels of the product, it is advantageous to ensure that the perfume is used efficiently.

A particularly preferred way to ensure that the perfume is used efficiently is to use an encapsulated perfume. The use of a perfume that is encapsulated reduces the amount of perfume vapor produced by the composition before it is diluted. This is important when the perfume concentration increases to allow the amount of perfume per wash to be maintained at a reasonably high level.

It is even more preferable that the perfume is not encapsulated, but also that the encapsulated perfume be provided with a deposit aid to increase the efficiency of the perfume deposit and the retention in the fabrics. The reservoir auxiliary is preferably attached to the encapsulation by means of a covalent bond, matted or strong adsorption, preferably by covalent or entangled bond.

Shading pigments

The shading pigment can be used to improve the performance of the composition used in the process of the present invention. The deposition of the shading pigment on the fabric improves when used in the compositions of the invention and in accordance with the process of the invention. Preferred pigments are violet

or blue It is believed that the deposit on low-level fabrics of a pigment of these shadows masks the yellowing of the fabrics. An additional advantage of shading pigments is that they can be used to mask any yellow dye in the composition itself.

Suitable and preferred classes of pigments are disclosed below:

Direct pigments:

Direct pigments (otherwise known as substantive pigments) are the kind of water-soluble pigments that have an affinity for fibers and are directly captured. Direct violet and direct blue pigments are preferred. Preferably bis-azo or tris-azo pigments are used.

More preferably, the direct pigment is a direct violet of the following structures:

5 in which:

the D and E rings can be, independently, naphthyl or phenyl, as shown;

R1 is selected from: hydrogen and C1-C4 alkyl, preferably hydrogen;

R2 is selected from: hydrogen, C1-C4 alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

R3 and R4 are independently selected from: hydrogen and C1-C4 alkyl, preferably hydrogen or methyl;

X and Y are independently selected from: hydrogen, C1-C4 alkyl, C1-C4 alkoxy, preferably the pigment has X = methyl; and

Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

15 Preferred pigments are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51 and direct violet 99. Pigments may be used that they contain bis-azo copper such as direct violet 66. The benzidene-based pigments are less preferred. In another embodiment, the direct pigment may be covalently bound to the photobleach, for example as described in WO2006 / 024612.

Preferably, the direct pigment is present from 0.000001 to 1% by weight, more preferably from 0.00001% by weight to 0.0010% by weight of the composition.

Acid Pigments:

Acidic cotton pigments provide benefits to garments that contain cotton. Preferred pigments and pigment mixtures are blue or violet. Preferred acid pigments are:

25 (i) azine pigments, in which the pigment is of the following nuclear structure:

wherein Ra, Rb, Rc and Rd are selected from: H, to a branched or linear C1 to C7 alkyl chain, a benzyl, a phenyl and a naphthyl;

The pigment is substituted with at least one SO3-or -COO- group.

ring B does not carry a group with a negative charge or a salt thereof;

and ring A may be further substituted to form a naphthyl;

The pigment is optionally substituted with groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.

Preferred azine pigments are: acid blue 98, acid violet 50 and acid blue 59, more preferably acid violet 50 and acid blue 98. Other preferred non-azine acid pigments are acid violet 17, acid black 1 and acid blue

29.

Preferably, the acid pigment is present at 0.0005% by weight to 0.01% by weight of the formulation.

Hydrophobic pigments:

The composition may comprise one or more hydrophobic pigments selected from benzodifurans, methine, triphenylmethanes, maftalimides, pyrazole, naphthoquinone, anthraquinone and chromophores of mono-azo or di-azo pigments. Hydrophobic pigments are pigments that do not contain any solubilizing group in charged water. Hydrophobic pigments can be selected from the groups of dispersed pigments and solvents. Blue and violet anthraquinone and mono-azo pigment are preferred.

Preferred pigments include solvent violet 13, dispersed violet 27, dispersed violet 26, dispersed violet 28, dispersed violet 63 and dispersed violet 77.

Preferably, the hydrophobic pigment is present at 0.0001% by weight to 0.005% by weight of the formulation.

Basic Pigments:

Basic pigments are basic pigments that carry a positive net charge. They are deposited on cotton. They are of particular utility for use in compositions containing predominantly cationic surfactants. The pigments can be selected from the basic violet and basic blue pigments in the International Color Index. Preferred examples include triarylmethane basic pigments, methane basic pigment, anthraquinone basic pigments, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; Basic Blue 3, Basic Blue 75, Basic Blue 95, Basic Blue 122, Basic Blue 124, Basic Blue 141.

Reactive pigments:

Reactive pigments are pigments that contain an organic group capable of reacting with cellulose and binding the pigment to cellulose with a covalent bond. They are deposited on cotton.

Preferably, the reactive group is hydrolyzed or the reactive group of the pigments has reacted with an organic species, such as a polymer, so that the pigment binds to this species. The pigments can be selected from the reactive violet and reactive blue pigments in the International Color Index list.

Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.

Pigment Conjugates:

Pigment conjugates are formed by direct bonding of acidic or basic pigments, to polymers or particles by physical forces. Depending on the choice of polymer or particle they are deposited on cotton or synthetic fabrics. A description is provided in WO2006 / 055787.

Particularly preferred pigments are: direct violet 7, direct violet 9, direct violet 11, direct violet 26,

direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, dispersed violet 27 dispersed violet 26, dispersed violet 28, dispersed violet 63, dispersed violet 77 and mixtures thereof.

Shading pigment may be used in the absence of a fluorescent agent, but it is especially preferred to use a shading pigment in combination with a fluorescent agent, for example to reduce yellowing due to chemical changes in the adsorbed fluorescent agent.

Structuring and kidnappers

The detergent compositions may also optionally contain relatively low levels of organic detergent structurant or sequestering material. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxidisuccinic acid, methyl acid, benzene polycarboxylic acids and citric acid. Other examples are DEQUEST ™, organic phosphonate sequestering agents marketed by Monsanto and alkenohydroxy phosphonates.

Other suitable structuring agents include the high molecular weight polymers and copolymers known because it has structuring properties. For example, such materials include polyacrylic acid, polyimaleic acid and suitable polyacrylic / polyamleic copolymers and salts thereof, such as those marketed by BASF under the SOKALAN ™ brand.

If used, the organic structuring materials may comprise from about 0.5% to 20% by weight, preferably from 1% by weight to 10% by weight of the composition. The preferred level of structuring is less than 10% by weight and, preferably, less than 5% by weight of the composition. A preferred scavenger is HEDP (1-hydroxyethylidene -1,1, diphosphonic acid), marketed, for example, as Dequest 2010. Also suitable but less preferred because it provides lower cleaning results is Dequest® 2066 (diethylenetriamine penta acid (phosphonic methylene) ) or heptasodium DTPMP).

Hydrotropes

The compositions preferably comprise one or more hydrotropes; although the minimum amount consistent with the need for concentration should be used. Suitable hydrotropes include MPG (monopropylene glycol). This and other conventionally used hydrotropes can be used in the composition at levels of 2 to 10% by weight. In the context of the present invention, a hydrotrope is a solvent that is not water or a conventional surfactant that aids in the solubilization of the surfactants and other components in the aqueous liquid to make it isotropic. In addition to MPG, among the suitable hydrotropes, glycerol, sodium cumene sulfonate, ethanol, other glycols, for example dipropylene glycol, diesters and urea may be mentioned as preferred.

Tampons

The presence of a buffer is preferred to control the pH; Preferred buffers are MEA and TEA. If present, they are preferably used in the composition at levels of 5 to 15% by weight.

External Structuring

The rheology of the compositions can be modified by using a material or materials that form a structuring network within the composition. Suitable structuring agents include hydrogenated castor oil, microfibrous cellulose and natural structuring agents such as citrus pulp fiber. Citrus pulp fiber is particularly preferred, especially if the enzyme lipase is included in the composition.

Visual indications

The compositions may comprise, and preferably do, visual indications of solid material that is not dissolved in the composition. They are preferably used in combination with an external structurant to ensure that they remain in suspension. Preferred visual indications are lamellar indications formed with polymeric film and, possibly, comprising functional ingredients that may not be as stable if exposed to the alkaline liquid. Enzymes and bleaching catalysts are examples of such ingredients. Also perfumes, particularly microencapsulated perfumes.

Packaging and dosage

Liquids can be packaged in unit doses. To allow greater flexibility in dosing, liquids are preferably supplied in multi-purpose plastic containers with an upper or lower closure. A dosing system can be supplied with the container either as part of the lid or as an integrated system.

Use procedure

Following the teachings of WO2009 / 153184, liquids according to the invention can be formulated so that they can be dosed in a typical automatic front loading washing machine at a dose level of 20 ml. The low level of surfactant during washing is compensated with the presence of enzymes, dirt-releasing polymers and EPEI together with optional high-efficiency cleaning ingredients, such as enzymes. However, the invention is also suitable for more conventional dosage levels of approximately 35 ml. To obtain suitable detergent liquids of this type, all that is needed is to add more water and possibly perfume to the 20 ml composition before packaging.

Fabric and fabric conditioner

The effect applies to all types of fabrics analyzed, in particular polyester, cotton and mixtures of these types of fibers or fabrics. The fabric conditioning active substance may be any of the known cationic softening active substances, in particular quaternary ammonium compounds, including biodegradable quaternary ammonium ester active substances; preferably hardened tallow quaternary triethanolamine. Fabric conditioners comprising imidazolines will also form complexes with an anionic surfactant and the invention also extends to washing fabrics that have previously been treated with a fabric conditioner comprising this type of fabric conditioning active substance.

The invention will be described below with reference to the following non-limiting examples.

Examples

The following materials are used in the examples:

LAS acid

is C12-14 linear alkylbenzenesulfonic acid

Fatty acid

is Prifac® 5908ex Croda saturated lauric fatty acid.

SLES 3EO

it is sodium lauryl ether sulfate with 3 moles of EO.

Empigen® BB

It is a former Huntsman alkyl betaine (coconut dimethylcarbobetaine).

NI 7EO

it is non-ionic C12-15 7EO Neodol® 25-7 alcohol ethoxylate (ant. Shell Chemicals).

Stenol 1618L

it is C16 / 18 non-ionic fatty alcohol ant. Cognis

Genepol C200

It is 20 non-ionic EO ant. Clariant

HTTEAQ

it is hardened tallow quaternary triethanolamine (cationic fabric softener active substance).

MPG

It is monopropylene glycol.

TORCH

It is triethanolamine.

NaOH

it is 47% sodium hydroxide solution.

EPEI

en Sokalan HP20 - ethoxylated polyethyleneimine cleaning polymer: PEI (600) 20EO ant. BASF

SRP

it is a dirt-releasing polymer (Texcare SRN 170 ant. Clariant)

Dequest® 2066

it is diethylenetriamine penta (methylene phosphonic) acid or (heptasodium DTPMP) ant. Thermphos

Fragrance

It is perfume without oil.

The fabric conditioner

The fabric conditioner used for the examples was a commercially available concentrated fabric conditioning composition marketed as the "Comfort" brand in the United Kingdom and dried in hardened tallow TEAQ. The fabric conditioner formulation is provided in Table 1. The fabric conditioner was used at the recommended dose for this 55 mls concentrated fabric conditioner.

Table 1 - Fabric conditioning composition

Ingredient

Quantity (100% active)

HTTEAQ

12.7

Stenol 1618L

1.00

Ingredient

Quantity (100% active)

Genepol C200

0.38

Perfume (without oils)

0.79

Minority substances and water, defoamers and pH modifier

including preservatives, Up to 100

Detergent liquids

Tables 2 to 4 show two detergents of the prior art and 4 liquids suitable for use in the invention. Compositions 1 to 4 for use in the invention are provided in Table 2. In the package of the

5 Comparative composition A (Ariel Excel gel with biological action), a commercially available detergent liquid marketed in the United Kingdom, is indicated to have the composition provided in Table 3. The package further recommends that it be dosed at 37 ml per wash. Comparative composition B (Persil Small and Mighty Biological) a commercially available detergent liquid commercialized in the United Kingdom has the composition provided in Table 4. It is recommended to dose at 35 ml per wash.

10 Table 2-Compositions 1-4

Liquid dose of 35 ml 20ml liquid dose

Example

one 2 3 4

% active

24 17.1 24 17.1

Ingredient

b24% to 17.10% b24% to 17.10%

MPG

twenty twenty twenty twenty

TORCH

0 0 0 0

Citric acid

0 0 0 0

NaOH

1.5 1.01 2,625 1.7675

NI 7 EO

10.55 7.28 18.4625 12.74

LAS acid

7.02 4.85 12,285 8.4875

Fatty acid

2.46 1.7 4,305 2,975

SLES (3EO)

3.5 2.42 6,125 4,235

Empigen® BB

0.86 0.86 1,505 1,505

EPEI

3.1 3.1 5,425 5,425

SRP

2.1 2.1 3,675 3,675

Dequest® 2066

0 0 0 0

Fragrance

1.39 1.39 2.4325 2.4325

Protease

1.35 1.35 2.3625 2.3625

Amylase

0.54 0.54 0.945 0.945

Mananasa

0.4 0.4 0.7 0.7

Table 3 - Comparative composition A

Ingredient

Quantity (%)

Anionic surfactant

> 30

Soap

5 -15

Nonionic

<5

Water, phosphonates, optical brighteners, enzymes, perfume and minor substances

Up to 100

According to the additional published information from the supplier (P&G), it is believed that the surfactant system consists of MEA-dodecylbenzenesulfonate (LAS neutralized with MEA), sodium laureth sulfate (SLES) and MEA5 palm kernelate.

In addition to water, the published information also suggests that the composition also includes: MEA citrate, C12-14 pareth-7 (non-ionic / emulsifier), PEI-ethoxylate, trimonoethanolamine etidronate, propylene glycol, MEA-Borate, glycosidase, sodium sulfate, diestierolbiophenyldisulfonate disodium, ethanolamine, protease, calcium chloride, dye and perfume.

10 Table 4 - Comparative composition B

Ingredient

Quantity (%)

LAS acid

13.40

SLES (3EO)

6.70

NI 7EO

20.12

NaOH

2.70

TORCH

3.23

Fatty acid

4.78

MPG

9.00

Glycerol

5.00

Dequest® 2066

0.50

Citric acid

0.98

Optical brightener

0.10

Protease

1.35

Amylase

0.54

Mananasa

0.40

Perfume (without oils)

1.39

Water and minor substances, including dyes

Up to 100 %

Example 1-Performance Evaluation

The experiment described below was designed to determine the impact of the use of the usual rinse conditioner on stain removal in subsequent washings.

Table 5 - Products analyzed and dose

Example

Dose / ml

TO

37

B

35

one

35

2

35

Washing was done in a European Miele washing machine using the conventional 30 ° C cotton washing cycle. The main wash was 15 l of water at room temperature of 261FH (Ca: Mg 3: 1) and the total wash time (including rinses) was 1 hour 56 minutes. A mixed ballast load of 3 kg (40% polyester had, 30% cotton had, 30% knitted cotton) was also included in each cycle to better similar the actual washing use conditions.

Two washing processes were used:

Process 1-Prewash treatment only

Each of the products in Table 5 was used to wash a ballast load as described above along with a series of cotton and polyester scraps that were to be stained afterwards. After washing, all fabrics were dried in a dryer. After two complete wash cycles, the scraps were soiled using a series of soils. Then a final wash treatment was performed on the stained scraps using the same ballast and the same washing conditions as before.

Process 2-Prewash and rinse with conditioner treatments

Each of the products in Table 5 was used to wash a ballast load as described above along with a series of cotton and polyester scraps that were to be stained afterwards. In this process, 55 ml of fabric conditioner detailed in Table 1 was added to the final rinse of each wash. After washing, all fabrics were dried in a dryer. After two complete wash cycles, the scraps were soiled using a series of soils. Then a final wash treatment was performed on the stained scraps using the same ballast and the same washing conditions as before. After the last wash no rinse conditioner was used.

Assessment

After washing, the stained scraps were dried in line in the dark before assessing the removal of the spots.

Before and after washing, the color of the spots was measured on a flatbed scanner and expressed in terms of the difference between the stained and clean cloth (wash), giving values of ΔE * (before washing) or ΔE * (after wash), respectively. The values of ΔE being the difference in color defined as the Euclidean distance between the stained and clean cloth in the color space L * a * b *. The values of ΔE * (after washing) became values of the Stain Removal Index (SRI) by applying the standard transformation.

SRI = 100 -ΔE * (after washing)

The impact of the rinse condition treatment was determined by measuring the yield loss of each composition analyzed when used together with the rinse conditioner (process 2) with respect to that obtained in the absence of rinse conditioner (process 1). Table 6 shows the SRIs without using the rinse conditioner. Table 7 shows the revised SRI when rinse conditioner is used as part of the pretreatment and the change in the SRI (process 1-process 2) is provided for the complete set of spots in table 8. AT stands for knitted cotton. PT means knitted polyester.

Table 6-Stain removal-prewash without rinse conditioner (process 1)

TO B one 2

stain

SRI Lsmeans SRI Lsmeans SRI Lsmeans SRI Lsmeans

PT ragout / sunflower oil

99.4 98.6 98.8 98.6

PT tomato (Pomarola) / sunflower oil

98.6 97.9 99.4 99.5

TO B one 2

stain

SRI Lsmeans SRI Lsmeans SRI Lsmeans SRI Lsmeans

PT red pepper / oil / water

98.5 96.6 99.4 99.3

PT Red Curry (Osman)

98.8 98.0 99.6 99.5

PT Facial makeup 2

99.2 99.1 99.2 99.3

AT 1: 1 garden dirt: Water

87.4 87.0 87.3 87.2

AT black tea

88.2 82.1 82.3 82.5

AT with mechanical grease

54.6 55.7 54.1 54.3

AT cocoa / milk

96.2 90.9 87.9 87.8

AT Facial makeup 2

94.2 91.5 92.0 90.2

AT Red Curry (Osman)

78.0 77.1 76.3 75.0

Yellow clay AT for pots 2: 1

82.8 80.5 79.8 77.6

AT chocolate cake (Heinz)

92.8 92.2 92.0 91.7

AT of red clay for pots 2: 1

78.2 74.0 76.2 76.8

AT chocolate ice cream (Economy)

92.7 86.7 86.9 87.3

AT blood (hemoglobin)

87.6 86.3 85.5 85.7

Total values of the SRI

1427.0 1394.1 1396.7 1392.3

Table 7-Stain removal-prewash with rinse conditioner (process 2)

TO B one 2

stain

SRI Lsmeans SRI Lsmeans SRI Lsmeans SRI Lsmeans

PT ragout / sunflower oil

82.7 77.9 97.0 98.1

PT tomato (Pomarola) / sunflower oil

89.7 89.0 99.3 99.4

PT red pepper / oil / water

89.9 84.4 99.4 99.3

PT Red Curry (Osman)

92.8 88.3 99.6 99.5

PT Facial makeup 2

93.4 91.0 99.0 99.2

AT 1: 1 garden dirt: Water

82.9 89.1 88.6 87.2

AT black tea

84.8 82.6 82.7 82.6

AT with mechanical grease

53.0 58.1 54.9 57.2

AT cocoa / milk

94.7 94.4 90.4 90.1

AT Facial makeup 2

92.8 93.4 91.9 92.4

AT Red Curry (Osman)

76.7 76.3 77.1 77.6

Yellow clay AT for pots 2: 1

82.7 78.5 81.5 83.2

AT chocolate cake (Heinz)

93.8 94.5 94.8 96.3

AT of red clay for pots 2: 1

79.3 78.9 79.8 83.6

TO B one 2

stain

SRI Lsmeans SRI Lsmeans SRI Lsmeans SRI Lsmeans

AT chocolate ice cream (Economy)

94.5 89.2 90.5 93.5

AT blood (hemoglobin)

90.1 95.4 93.6 95.7

Total revised SRI values

1373.8 1360.9 1420.1 1434.7

Table 8-Stain Removal-Difference in SRI -ΔSRI

TO B one 2

stain

ΔSRI Lsmeans ΔSRI Lsmeans ΔSRI Lsmeans ΔSRI Lsmeans

PT ragout / sunflower oil

-16.7 -20.7 -1.8 -0.5

PT tomato (Pomarola) / sunflower oil

-8.9 -8.9 -0.2 -0.1

PT red pepper / oil / water

-8.6 -12.2 0.0 0.0

PT Red Curry (Osman)

-5.9 -9.7 0.0 0.0

PT Facial makeup 2

-5.8 -8.0 -0.2 -0.1

AT 1: 1 garden dirt: Water

-4.5 2.1 1.3 -0.1

AT black tea

-3.4 0.4 0.4 0.1

AT with mechanical grease

-1.6 2.4 0.8 2.9

AT cocoa / milk

-1.5 3.5 2.5 2.3

AT Facial makeup 2

-1.4 1.9 -0.1 2.2

AT Red Curry (Osman)

-1.3 -0.7 0.8 2.6

Yellow clay AT for pots 2: 1

-0.1 -2.0 1.7 5.6

AT chocolate cake (Heinz)

1.0 2.3 2.8 4.6

AT of red clay for pots 2: 1

1.1 4.9 3.6 6.8

AT chocolate ice cream (Economy)

1.9 2.5 3.6 6.2

AT blood (hemoglobin)

2.5 9.1 8.1 10.0

-53.2 -33.3 23.4 42.4

Grease / oil stains: Ragout / sunflower oil, tomato (Pomarola) / sunflower oil, red pepper / oil / water, 5 red curry (Osman), facial makeup. Mechanical grease

Particle spots: AT 1: 1 garden dirt: Water, yellow clay pot 2: 1, soybean clay pot 2: 1

Sequestrant stains: Black tea

Enzymatic stains: cocoa / milk, chocolate cake (Heinz), chocolate ice cream (Economy), blood (hemoglobin).

The data shows that the compositions are used according to the invention exhibit a much greater solidity to clarify the presence of conditioner than the comparative compositions of the prior art with higher levels of surfactants during washing. When there are reductions in performance over the addition of conditioner, these are reduced. When there are benefits from the addition of conditioner, these are amplified.

There are several significant gains with oil / grease stains on polyester. There is an approximate parity on enzyme and particle spots. The performance on the sequestrant stains is unexpectedly as good, or better, than that of the comparative compositions.

Regarding composition 2 versus comparative composition B: there are significant gains with spots

5 oil / grease, especially on polyester. There are significant gains with particle spots and there is a parity on enzymatic / bleachable / sequestering spots. The effects are greater with oil / grease stains on polyester.

Composition 2 versus comparative composition A shows superiority with grease / oil stains over polyester. The same slight downward trend compared to B is observed in cotton (2 results

10 significant). Enzymatic and particle spots give approximate parity.

When the levels of higher surfactants used in composition 1 are compared with the results obtained for composition 2, the benefit of using lower levels of non-soap surfactants during washing is observed. Composition 2 performs better than composition 1 when used after the rinse conditioner.

Claims (9)

1. A process for washing fabrics on which a cationic fabric softener active substance has been deposited and dried, comprising the step of contacting the fabric with an aqueous wash liquor having the following composition: 5 a) 15 to 600 ppm of non-soap surfactant, b) at least 50 ppm of ethoxylated polyethyleneimine, c) at least 25 ppm of polyester dirt release polymer, The total polymer level (b + c) being at least 20% by weight of the level of the surfactant not Soapy (a), 10 d) from 0.1 to 100 ppm of enzyme selected from protease, amylase, cellulase, and e) optionally, the enzyme lipase. 2. A process according to claim 1, wherein the level of the non-soap surfactant (a) is from 200 to 400 ppm. 3. A process according to any of the preceding claims, wherein the non-soap surfactant (a) comprises at least 50 ppm of anionic surfactant.

Four.

A process according to any of the preceding claims, wherein the EPEI is non-ionic.

5.

A process according to any of the preceding claims, wherein the cationic fabric softener active substance is a quaternary ammonium compound.

6.

A process according to any of the preceding claims, wherein the polymer releasing

Polyester dirt (c) is non-ionic and comprises a substantive core polyester block of terephthalate repeat units and one or more terminal blocks of polyethylene glycol with a minor alkyl or a hydrogen moiety at its end. 7. A process according to any of the preceding claims, wherein the washing liquor is form by adding to the water dose of 15 to 40 ml of an aqueous liquid detergent composition and diluting by a factor of at least 600.

8.

A process according to any one of the preceding claims, wherein the non-soap surfactant comprises LAS, SLES and non-ionic ethoxylated fatty alcohol.

9.

A process according to any one of the preceding claims, wherein the non-soap surfactant comprises carbobetaine.