ES2587861T3 - Isotropic liquid detergents comprising soil release polymer - Google Patents

Abstract

An isotonic liquid detergent composition with a bottle pH in the range 6.0 to less than 7, the composition comprising, in addition to water: a) up to 60% by weight detersive surfactant including at least 5% by weight anionic sulfonate and / or sulfate surfactant comprising surfactant acid neutralized with one or more materials, the pKa of whose conjugated acid / s is more than 2 units higher than the bottle pH of the liquid detergent composition b) at less 0.3% by weight of fatty acid partially neutralized with one or more materials the pKa of whose conjugated acid / s is more than 2 units higher than the bottle pH of the liquid detergent composition - c ) at least 1.0% by weight, preferably at least 1.8% by weight, of triethanolamine (TEA); and d) at least 0.5% by weight of Soil Release Polymers (SRP); provided that the composition is not one of the compositions (A), (B) or (C): (A) a composition consisting of 8.49% by weight of linear C12-14 alkylbenzene sulfonic acid, 4.24 % by weight of sodium lauryl ether sulfate with 3 moles EO, 1.50% by weight of saturated lauric fatty acid Prifac® 5908, 12.74% by weight of ethoxylated alcohol C12-15 7EO nonionic Neodol® 25-7, 0 , 15% by weight of NaOH solution (47%), 3.50% by weight of triethanolamine, 20.00% by weight of monopropylene glycol, 5.46% by weight of Sokalan HP20 ethoxylated polyethylene imine polymer (PEI (600 ) 20 EO), 3.55% by weight of Texcare SRN 170 Soil Release Polymer, 2.43% by weight of oil-free perfume, and water up to 100% by weight; (B) a composition consisting of 8.49% by weight of C12-14 linear alkylbenzene sulfonic acid, 4.24% by weight of sodium lauryl ether sulfate with 3 moles EO, 1.50% by weight of saturated lauric fatty acid Prifac® 5908, 12.74% wt ethoxylated alcohol C12-15 7EO nonionic Neodol® 25-7, 0.15% wt NaOH solution (47%), 3.50% wt triethanolamine, 20 .00 wt% monopropylene glycol, 5.46 wt% Sokalan HP20 ethoxylated polyethylene imine polymer (PEI (600) 20 EO), 3.55 wt% Texcare SRN 170 Soil Release Polymer, 1.63 % by weight of Axis House RK 853 coconut hydroxamic acid, 2.43% by weight of oil-free perfume, and water up to 100% by weight; (C) a composition consisting of 8.49% by weight of C12-14 linear alkylbenzene sulfonic acid, 4.24% by weight of sodium lauryl ether sulfate with 3 moles EO, 1.50% by weight of saturated lauric fatty acid Prifac® 5908, 12.74% wt ethoxylated alcohol C12-15 7EO nonionic Neodol® 25-7, 0.15% wt NaOH solution (47%), 3.50% wt triethanolamine, 20 .00 wt% monopropylene glycol, 5.46 wt% Sokalan HP20 ethoxylated polyethylene imine polymer (PEI (600) 20 EO), 3.55 wt% Texcare SRN 170 Soil Release Polymer, 1.63 % by weight of Axis House RK 852 coconut hydroxamate K + salt, 2.43% by weight of oil-free perfume, and water up to 100% by weight.

Description

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

DESCRIPTION

Detergents Isotropic liquids comprising a quantity of dirt release Technical field

The present invention relates to isotonic liquid detergent compositions comprising water, hydrotrope, anionic sulphonate or sulfate surfactant and a polyester based on soil release polymers.

Background

WO09153184 suggests that a liquid laundry detergent concentrate can be designed by substituting a surfactant with a mixture of more weight efficient ingredients selected from polymers and enzymes. A preferred composition utilizes a combination of ethoxylated imine polyethylene (EPEI) and a polyester polymer soil release polymer (SRP) to achieve an excellent detergency of particulate and oily dirt at significantly lower levels of washing surfactant than is normally supplied from a high performance liquid. The compositions illustrated comprise anionic surfactant comprising linear alkyl benzene sulphonate neutralized with sodium hydroxide and further comprise soap formed by the neutralization of fatty acid by sodium hydroxide. The compositions are alkaline. It has been found that SRP used for the examples suffers from alkaline hydrolysis and that it is catalyzed by the use of triethanolamine (TEA) in the compositions.

An obvious solution to the problem of SRP hydrolytic instability is to divide the composition and store it in separate compartments so that the SRP does not come into contact with ASD or alkalinity. Such partial acid-based formulations may be based on teaching in EP294893, US2010229313, and US3893929. However, the use of division compositions is not desirable, since it adds cost and complexity. Consumers want to have all the cleaning supplied from a single main wash liquid.

There is considerable technical damage against the formulation of main washing liquids that are acidic. It is widely believed that acidic washing conditions will result that lead to improper cleaning due to reduced performance of the surfactant system and possibly some of the enzymes. Document US5290475 (Colgate) is a document that shows the technical prejudice against the formulation under acidic conditions in order to increase the stability of the SRP. A composition of non-ionic detergent antistatic and liquid softener comprises as essential ingredients a non-ionic detergent, an anionic detergent, an antistatic softening agent of cationic tissues and a polymer promoting the release of dirt from a water soluble fraction of the polyethylene terephthalate type - polyoxyethylene terephthalate. To aid in the solubilization of detergents and optical brighteners that may be present in liquid detergents, a small proportion of alkaline material or a mixture of such materials is often included. Suitable alkali materials include mono-, di- and trialkanolamines, alkyl amines, ammonium hydroxide and alkali metal hydroxides. Of these preferred materials are alkanolamines, preferably t-canolamines and of these especially triethanolamine. The pH of the final liquid detergent, which contains said basic material will normally be neutral or slightly basic. Satisfactory pH ranges are from 7 to 10, preferably about 7.5 to 9.5.

WO9742286 (P&G) teaches in p3 that laundry detergents typically have a pH greater than 7.5. According to compositions containing SRP p9, it discloses a pH of about 7.2 to about 8.9 when measured as a 10% solution in water.

US4785060 (Colgate) describes high molecular weight PET POET SRP manufactured using a mixed catalyst system. It is said that these SRPs retain their performance at a high wash pH in the presence of a detergency builder. It is taught that they are included in both solid and liquid detergent compositions. The description teaches to minimize the inclusion of alkanolamines such as TEA and ionizable salts such as Na. It is taught in column 10 lines 13 to 15 that it is preferred that the neutralizing agent employed, generally to increase the pH of the liquid detergent mixture, be sodium hydroxide. In lines 17 to 18 he continues saying that "triethanolamine and free triethanolamine salts in general should be avoided". The pH will be in the range of 6 to 10, preferably 6.1 to 8.9 and often more preferably 6.5 to 7.5.

Document US4759876 ('876) (Colgate) discloses a liquid detergent composition that releases dirt that comprises SRP. The composition also comprises a stabilizing ratio of an enzyme stabilizer that also acts as a buffer for the liquid detergent composition to maintain the pH in a certain neutral or slightly acidic range to stabilize the SRP and the fluorescent brightener. It is said that the composition "substantially retains" its characteristic promoters of dirt release and hydrolyzing fluorescent polishing of the dirt in storage so that the laundry washed therewith is cleaned, brightened and effectively treated. However, document US5110506, of the same assignee, shows that the performance was not as good as suggested by '876. In addition, it is evident from the description of '876 that the pH becomes acidic during storage. We have determined that this is likely to be due to the rupture of the SRP since it is hydrolyzed for a month of storage. None included

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

soap. The enzyme stabilizer / buffer is said to maintain the pH at 6.2 or higher. A pH range of 6.2 to 6.5 is provided after storage. However, an additional pH range of 5.8 to 7 is also given as one that does not destabilize the polymer.

In US5110506 (Colgate) in addition to the revelation that the liquid of '876 gave low dirt removal performance after storage it is taught that a small improvement in the dirt release performance after storage can be achieved by changing from the non-ionic to a very expensive special that minimizes the content of 2OE and 3OE. It is taught that the liquid detergent has a pH in the range of 7.3 to 8.1. This indicates that the pH is still drifting due to hydrolysis. The supposed improvement in cleaning is probably due to the change with the most effective type of non-ionic surfactant.

GB1466639 (P&G) discloses liquid detergents with surfactant neutralized with ethanolamine and SRP. Some free ASD is included to maintain alkaline wash water. Two different types of liquids are disclosed. In the first type the specific non-ionic surfactant selected provides sufficient physical stability of the composition. In the second type, fatty acid (soap) is included to provide long-term storage stability. Example 1 seems to be an example of the second type of composition. It comprises 1.5% TEA salt of oleic acid and 5% SRP (from table 1). It is discovered that the composition is alkaline.

US4411831 (Purex) discloses a stable aqueous detergent composition that has improved soil release properties and essentially consists of SRP with LAS and non-ionic and a buffer sufficient to maintain the pH of the aqueous composition within the Range of 5, 0 to 9.0, preferably 6.5 to 7.5. The examples used ZELCON 4780 SRP in a main wash composition comprising LAS and non-ionic and the pH adjusted to 7. SXS was used as a hydrotrope. No TEA or soap was used in the examples. The description teaches that comparative liquids without buffer generate an acidic pH during storage. The acidic pH is said to be harmful to brighteners. We understand that acidic pH is generated due to the decomposition of the SRP. The solution adopted is to add a buffer to stabilize the pH. This will result in an increase in the decomposition of the SRP because the pH is more alkaline. The brightener can be protected and this seems to be the real objective of this disclosure. It is taught that suitable buffers include bicarbonates, orthophosphate borates and alkanolamine hydrochlorides.

Document US4713194 (P&G) discusses the vulnerability of SRP to degradation in alkaline environments and proposes to protect the SRP by wrapping if it is to be used in granular compositions, or by adjusting the pH of the product so that it is between 7.0 and 8.5 if it is to be used in liquid compositions. The examples contain coconut fatty acid at high levels.

US6262007 (P&G) describes acidic detergent liquids, which include SRP to reduce the increase in viscosity as the temperature drops. Some examples include ASD, but no hydrotrope or fatty acid.

There is a need for concentrated liquid detergent compositions comprising SRPs that provide excellent cleaning, even after prolonged storage.

Summary of the invention

According to the present invention, an isotonic liquid detergent composition is provided with a bottle pH in the range 6.0 to less than 7, the composition comprising, in addition to water:

a) up to 60% by weight of detersive surfactant including at least 5% by weight of anionic sulphonate and / or sulphonate surfactant comprising surfactant acid neutralized with one or more materials the pKa of whose conjugate acid (s) more than 2 units higher than the bottled pH of the liquid detergent composition

b) at least 0.3% by weight partially neutralized fatty acid with one or more materials the pKa of which conjugated acid (s) is more than 2 units higher than the pH in the bottle of the liquid detergent composition

c) at least 1.0% by weight, preferably at least 1.8% by weight, of Triethanolamine (TEA); Y

d) at least 0.5% by weight of soil release polymers (SRP);

provided that the composition is not one of the compositions B, 1 or 2 disclosed in EP 2 522 714 A1.

According to another embodiment of the present invention an isotropic liquid composition of packaged detergent is provided with a pH in the bottle in the range 6.0 to less than 7, where the composition comprises, in addition to water:

a) up to 60% by weight of detersive surfactant including at least 5% by weight of anionic sulphonate and / or sulphonate surfactant comprising surfactant acid neutralized with one or more materials the pKa of whose / s

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

Conjugated acid (s) is more than 2 units higher than the pH in the bottle of the liquid detergent composition;

b) at least 0.3% by weight of partially neutralized fatty acid with one or more materials, the pKa of whose conjugate acid (s) is more than 2 units higher than the pH in the liquid composition of the liquid Detergent

c) at least 1.0% by weight, preferably at least 1.8% by weight, of triethanolamine (TEA); Y

d) at least 0.5% by weight of dirt release polymers (SRP).

Preferably the composition has a pH in the bottle of 6.3 to 6.7. By bottle we refer to any container package in which the liquid is stored. It could be a plastic package in the form of a bottle, squeezable or nested, stored in a vertical or inverted position, or a unit dose format such as a soluble bag, or a sachet.

Fatty acid provides buffering capacity but its inclusion leads to phase separation of acidic compositions at low temperature. Therefore, it can only be included in relatively low levels. It cannot be totally eliminated as a material used to neutralize the anionic surfactant a), preferably sodium hydroxide or monsetanolamine (MEA), it cannot stabilize the composition by itself. Preferably the fatty acid is saturated. Much more preferably it is used in an amount of 0.5 to 1.5% by weight.

The use of ASD helps the stability of fatty acid and therefore ASD is included at a level as high as can be tolerated by the SRP. The amount of ASD is preferably up to 3.7% by weight, and much more preferably is in the range 2.0 to 3.5% by weight.

Advantageously, one or more materials, the pKa of whose conjugate acid (s) is more than 2 units higher than the pH in the bottle of the liquid detergent composition comprises 0.08 to 0.25% by weight of NaOH and / or monoethanolamine (preferably 0.1 to 0.23% by weight (MEA). This definition of the non-buffer component is intended to cover all common strong and weak bases outside the buffer region of interest (Slightly acidic: 6.0 unless 7) Thus, the material used to neutralize the anionic acid surfactant to make anionic surfactant a), whose material the pKa of whose conjugate acid (s) is found more 2 units higher than the pH in the bottle of the liquid detergent composition, it does not act significantly as a buffer in the pH in the bottle in which the composition is stored, in contrast, the TEA acts as a buffer in the pH In slightly acidic bottle.

The SRP is the type that settles from the solution flooded in polyester. It preferably has a substantive polyester part formed by condensation of terephthalic acid ester and diol, preferably 1,2 propanediol, and also comprises a protected terminal hydrophilic part comprising repeated units of ethylene oxide protected with an alkyl group. It can be used in an amount of more than 0.5% by weight and can be present up to a level of 16% by weight. Mixtures of different SRPs can be used.

The liquid will typically comprise a hydrotrope. When used, the hydrotrope level will be at least 5% by weight, preferably at least 9% by weight, more preferably at least 14% by weight. For reasons of cost the amount of hydrotrope is preferably less than 25% by weight and much more preferably less than 20% by weight of the compositions. A preferred hydrotrope is 1.2 propanediol (MPG).

Advantageously, the composition comprises at least 3, preferably at least 5% by weight of ethoxylated imine (EPEI) polyethylene to improve removal of particulate dirt.

Detailed description of the invention

In addition to the essential features, the compositions of the invention may contain other ingredients. Such ingredients include viscosity modifiers, foam boosting agents, preservatives (eg bactericides), pH buffering agents, polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, coating promoting agents, anti-static agents and adjuvants. ironing, dyes, pearling agents and / or opacity agents, and darkening dye.

Aspects of the essential and optional aspects of the compositions are described below.

Isotropic Liquids

The amount of detersive surfactant forms at least 10% by weight of the total liquid composition, preferably forms from 12 to 60% by weight. The compositions according to the invention much more preferably have total levels of active detersive surfactant of at least 15% by weight.

The compositions may be concentrated compositions designed to be added to a 10 liter wash in small doses that need to be diluted in at least 500 times their own volume of water to form a main wash water comprising a maximum of 0.5 g / l of surfactant. They can also be compositions

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

Concentrates designed for hand washing or automatic top-loading washing machines. Less water can be used in hand washing and automatic top-loading washing machines. normally a greater amount of water is used. The dose of liquid detergent is adjusted accordingly to give similar wash water concentrations.

Surfactants

Surfactants help in removing dirt from the grid of textile materials also help keep the dirt removed in the solution or suspension in the wash water. 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 surfactant forms the mayone of the non-soap surfactant (a).

Anionics

The preferred sulfonated alkyl are alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates having an alkyl chain length of C8-C10.

Preferred linear alkyl benzene sulphonate surfactants are retail LAS with an alkyl chain length of 8 to 15, more preferably 12 to 14.

Further, it is desirable that the composition comprises an anionic polyethoxylated alkyl sulfate surfactant of the formula (I);

RO (C2H-, O) xSO3-M + (I)

where R is an alkyl chain having 10 to 22 carbon atoms, saturated or unsaturated, M is a cation that makes the compound water soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages 1 to fifteen.

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

Non ionic

Non-ionic surfactants include primary and secondary ethoxylated alcohols, especially ethoxylated C8-C20 aliphatic alcohol with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially C10-C15 primary and secondary aliphatic alcohols ethoxylated with a 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 therein, the composition contains from 0.2% by weight to 40% by weight, preferably 1% by weight to 20% by weight, more preferably 5 to 15% by weight of a non-ionic surfactant, such as ethoxylate of alcohol, nonylphenol ethoxylate, alkyl polyglycoside, alkyldimethylamineoxide, ethoxylated monoethanolamide fatty acid, monoethanolamide fatty acid, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").

Non-ionic surfactants that can be used include ethoxylates of primary and secondary alcohols, 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. C10-C15 secondary ethoxylates with an average of 1 to 10 moles of ethylene oxide per mole of alcohol.

Amine oxide

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

R1N (O) (CH2R2) 2

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

Preferred amine oxides have R1 is C8-C18 alkyl, and R2 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyldimethylamine oxide, octadecylamine oxide.

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

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

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

While in some of the preferred embodiments R2 is H, it is possible to have R2 slightly larger than H. Specifically, R2 can be CH2OH, such as: hexadecylbis (2-hydroxyethyl) amine oxide, tallow bis (2-hydroxyethyl) ) amine, stearylbis (2-hydroxyethyl amine) oxide and oleylbis (2-hydroxyethyl) amine oxide.

Preferred amine oxides have the formula:

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

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

Zwitterionics

Free non-ionic systems with Up to 95% by weight of LAS can be done on condition that some zwitterionic surfactant, such as carbobetama, is present. A preferred zwitterionic material is a carbobetama available from Huntsman under the name Empigen® BB. The carbobetamas improve the detergency of particulate dirt in the compositions of the invention.

Preferred compositions comprise at least 1% by weight of amine oxide or carbobetama or mixtures thereof. Additional surfactants

Other surfactants other than the preferred LAS, SLES, non-ionic and amphoteric surfactant (betama and / or amine oxide) can be added to the mixture of detersive surfactants. However, cationic surfactants are preferably substantially absent.

Although less preferred, some alkyl sulfate surfactant (PAS), especially primary and secondary C12-15 alkyl sulfates, non-ethoxylates may be used. A particularly preferred material, commercially available from Cognis, is Sulphopon 1214G.

Other polymer

EPEI

A particularly preferred class of polymers for use in combination with the polyester soil release polymer (SRP) is ethoxylated polyethyleneimine (EPEI). Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, when branched, the hydrogen in nitrogen is replaced by another chain of ethylene imine units. These polyethyleneimines can be prepared, for example, by polymerization of ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these main polyamine structures are disclosed in US Patent No. 2,182,306, Ulrich et al, issued December 5, 1939; U.S. Patent No. 3,033,746, Mayle et al, issued May 8, 1962; U.S. Patent No. 2,208,095, Esselmann et al, issued July 16, 1940; U.S. Patent No. 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent No. 2,553,696, Wilson, issued May 21, 1951.

Preferably, the EPEI comprises a main structure of polyethyleneimine of about 300 to about 10,000 of weight average molecular weight; in which the modification of the main structure of polyethyleneimine is intended to leave the polymer without quaternization and not ionic. Such non-ionic EPEI may be represented as PEI (X) YEO where X represents the molecular weight of unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the main polyethyleneimine structure. The ethoxylation can vary from 9 to 40 ethoxy moieties by modification, preferably it is in the range of 16 to 26, much more preferably 18 to 22.

When used, the EPEI polymer is present in the composition preferably at a level of up to 25% by weight, and preferably at a level of at least 3% by weight more preferably from 4 to 15% by weight and much more preferably at minus 5% by weight. The ratio of non-soap surfactant and EPEI is from 2: 1 to 7: 1, preferably from 3: 1 to 6: 1, or even at 5: 1.

Other types of polymer

In addition to polyester dirt release polymers, dye transfer inhibitors, anti-redeposite polymers and cotton dirt release polymers can be used, especially those based on modified cellulosic materials.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

Hydrotrope

In the context of the present invention, a hydrotrope is a solvent that is neither water nor conventional surfactant that aids in the solubilization of the surfactants and other components in the aqueous liquid to be isotropic. Among the suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulfonate, ethanol, other glycols, for example, di propylene glycol, dieters and urea.

In addition to a tendency towards a more acidic composition pH in storage, which we attribute to the hydrolysis of the SRP, we have also observed that the physical stability of the composition also seems to be improved when it contains an SRP that is susceptible to alkaline hydrolysis; In particular, we have found that the SRP sold by Clariant under the trade name Texcare SRN170 is not stable when stored in an alkaline detergent composition and also the inclusion of this polymer in an alkaline detergent composition containing surfactant provides a surprising reduction in the viscosity of the composition. Even with the newly manufactured polymer this effect was observed. We believe that the SRP acts as a hydrotrope in the isotropic detergent liquid.

Enzymes

It is preferred that at least one or more enzymes may be present in the compositions. Preferably at least two, more preferably at least three different classes of enzymes are used in combination.

Lipase

Lipase is a particularly preferred enzyme. The composition may comprise about 50 to about 20,000 LU / g of a lipase. Preferably at least 800 LU / g. Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Examples of useful lipases include Humicola lipases, more preferably others comprising a polypeptide having an amino acid sequence that has at least 90% sequence identity with the wild type lipase derived from Humicola lanuginose, much more preferably the DSM strain 4109. The amount in the composition is higher than what is typically found in liquid detergents. This can be seen by the ratio of non-soap surfactant and lipase enzyme, in particular. A particularly preferred lipase enzyme is available under the trademark Lipoclean ™ of Novozymes.

As indicated above, appropriate lipases include those of bacterial or fungal origin. The genetically engineered or chemically modified mutants are included. Examples of useful lipases include Humicola lipases (synonymous Thermomyces), 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 of P. alkalgenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, strain of Pseudomonas sp. SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacilus 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 the wild-type lipase obtained from Humicola lanuginose.

Other examples are lipase variants 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.

Commercially available preferred lipase enzymes include Lipolase ™ and Lipolase Ultra ™, Lipex ™ and Lipoclean ™ (Novozymes A / S).

In addition to, or as an alternative to, lipase one or more enzymes may be present.

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

Preferred lipases include first wash lipases derived from the strain of Humicola lanuginosa DSM 4109 available under the Novozymes brand m Lipex ™. A similar Novozymes enzyme, but considered to be outside the above definition, is sold by Novozymes under the name Lipoclean ™ and this is also preferred.

Phospholipase:

The method 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 here, the term phospholipase is an enzyme that has enzymatic activity towards phospholipids. Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two acid

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

fatty in an external position (sn-1) and medium (sn-2) and are esterified with phosphoric acid in the third position; phosphoric acid, in turn, can be esterified in an amino alcohol. Phospholipases are enzymes that participate in the hydrolysis of phosphideptides. Several types of phospholipase activity can be distinguished, including phospholipases Ai and A2 that hydrolyse a fatty acyl group (at position sn-1 and sn-2, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) that can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacylglycerol or phosphatidic acid respectively.

Protease:

Suitable proteases include those of animal, plant or microbial origin. The microbial origin is preferred. Chemically modified or genetically engineered protein mutants are included. The protease can be a serine protease or a metalloase protease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred protease enzymes available in stores 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 method of the invention can be carried out in the presence of cutinase. classified in EC 3.1.1.74. The cutinase used according to the invention can be of any origin. The cutinases are preferably 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. Chemically modified or genetically engineered protein 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 sp. 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. Chemically modified or genetically engineered protein mutants are included. Suitable cellulases include cellulases of the Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium genera, for example, fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4.4, 7, US 4.4, 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:

Appropriate peroxidases / oxidases include those of plant, bacterial or fungal origin. Chemically modified or genetically engineered protein 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 from different bacterial genera such as Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis (Nasser et al (1993 ) FEBS Letts. 335: 319-326) and Bacillus sp. YA-14 (Kim et al (1994) Biochem Biosci Biotech 58: 947-949). The purification of pectate liases with maximum activity in the pH range of 8 to 10 produced by Bacillus pumilus (Dave and Vaughn (1971) J. Bacteriol 108: 166-174), B. polymyxa (Nagel and Vaughn (also described) 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. Sci Food. 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 liases independent of divalent and / or thermostable cations, can be used in the practice of the invention. In preferred embodiments, the pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1996) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al, (1995) Plant Physiol., 107: 963-976. Pectate lyases specifically contemplated are disclosed in WO 99/27083 and WO 99/27084. Other pectate lyases specifically contemplated (derived from Bao ilus Ilcheniformis) are disclosed in US Patent No. 6,284,524. Variants of pectate lyase specifically contemplated are disclosed in WO 02/006442, especially the variants disclosed in the examples in WO 021006442.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

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 filamentous fungus strain of the Aspergillus genera, preferably Aspergillus niger or Aspergillus aculeatus (WO 94/26576). WO 93/24622 discloses an isolated mannanase of T choderma reseei. Mananases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol. 56, No. 11, pages 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus. Mendoza et al., J. World Microbiol. Biotech., Vol. 10. No. 5, pages. 551-555 (1994) describes a beta-mannanase derived from Bacillus subtilis. JP-A-03047076 describes a beta-mannanase derived from Bacillus sp. JP-A-63056289 describes the production of a thermostable alkaline beta-mannanase. JP-A-63036775 refers to the Bacillus FERM P-8856 microorganism that produces beta-mannanase and beta-mannosidase. JP-A-08051975 discloses alkaline beta-mannanases of Bacillus sp. AM-001 alkalofflica. A purified mannanase from Bacillus amy loliquefaciens is disclosed in WO 97/11164. WO 91/18974 describes a hemicellulase such as an active substance of glucanase, xylanase or mannanase.

The mananasas of the alkaline family 5 and 26 derived from Bacillus agaradhaerens, licheniformis, Bacillus Bacill halodurans, Bacillus clausii, Bacillus sp., And Humicola insolens disclosed in WO 99/646 19. are especially contemplated. . involved 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 can show some kind of interaction and should be chosen in such a way that this interaction is not negative. Some negative reactions can be avoided by encapsulating one or the other of the enzyme and pro-fragrance and / or other segregation within the product.

Enzyme 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 ester of aromatic borate, or a derivative of phenyl boronic acid such as 4-formylphenyl boronic acid, and the composition can be formulated as described in for example, WO 92/19709 and WO 92/19708.

Lignin Compounds:

When a lipase enzyme is included, a lignin compound can be used in the composition in an amount that can be optimized by trial and error. Lignin is a component of all vascular plants, which are found in their mayone between cell structures, but also within cells and cell walls.

Preferably the lignin compound comprises a lignin polymer and more preferably it is a modified lignin polymer. A modified lignin polymer as used herein is lignin that has undergone a chemical reaction to covalently bind chemical moieties to lignin. The attached chemical moieties are preferably substituted at random.

Preferred modified lignin polymers are lignins that have been substituted with anionic, cationic or alkoxy groups, or mixtures thereof. Preferably the substitution occurs in the aliphatic part of lignin and is random. Preferably the modified lignin polymer is substituted with an anionic group, and preferably it is a sulphonate. A preferred cationic group is a quaternary amine. Preferred alkoxy groups are polyalkylene oxide chains having repeated units of alkoxy moieties in the range of 5 to 30, much more preferably ethoxy. Preferably the modified lignin sulfonate is substituted with anionic or alkoxy groups. The modified lignin polymers are discussed in WO / 2010/033743. Most preferably, the modified lignin polymer is lignin sulfonate (lignosulfonate). Lignin sulphonate can be obtained by the Howard process.

Illustrative lignin sulphonate can be obtained from a variety of sources including hardwoods, softwoods and effluent streams or recycling. Lignin sulphonate can be used in raw or pure forms, for example, in a condition "such as this" or a condition of total mother water, or in a form of purified lignin sulphonate from which or in which sugars and other removed components have been removed or destroyed, or from which or in which the inorganic components have been partially or totally eliminated. Lignin sulphonate can be used in salt forms including calcium lignin sulphonate, sodium lignin sulphonate, lignin ammonium sulfonate, potassium lignin sulphonate, magnesium lignin sulphonate and mixtures or

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

combinations thereof.

The lignin sulphonate preferably has a weight average molecular weight of 2000 to 100,000. Its basic structural unit is phenylpropane. The degree of sulfonation is preferably 0.3 and 1.0 sulfate groups per phenylpropane unit. Lignin sulphonate is available from a number of suppliers including Borregaard LignoTech, Georgia-Pacific Corporation, Lenzing AG and Tembec Inc. Lignin sulphonates are discussed in Lauten, RA, Myrvold, BO and Gundersen, SA (2010) New Developments in the Commercial Utilization of Lignosulfonates, in Surfactants from Renewable Re-sources (eds M. Kjellin and I. Johansson), John Wiley & Sons, Ltd, Chichester, UK.

Fluorescent Agents:

It is perhaps advantageous to include fluorescent agents in the compositions. Typically, these fluorescent 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 from 0.005 to 2% by weight, more preferably 0.01 to 0.5% by weight.

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

Preferred fluorescent agents are: 2- (4-styryl-3-sulfophenyl) 2H-naphthol [1,2-d] triazole sodium, disodium 4,4'-bis {[(4 anilino-6- (Nmethyl-N-) 2-hydroxyethyl) amino 1,3,5-triazin-2-yl)] amino} stilbene-2-2 'disulfonate, disodium

4,4'-bis {[(4-anilino-6-morpholino1,3,5-triazin-2-yl)] amino} stilbene-2-2 'disulfonate, and disodium 4,4-bis (2-sulfosliryl) biphenyl

Bleaching catalyst

The detergent compositions according to the invention may comprise a weight effective bleaching system. Such systems typically do not use the conventional percarbonate activator and bleach methodology.

The present invention can be used in a formulation that is used for bleaching through air, or an air bleaching catalyst system. Suitable complexes and organic molecule precursors (ligand) for complex formation are available to those skilled in the art, for example, from: WO 98/39098; WO 98/39406, WO 97/48787, WO 00/29537; WO 00/52124, and WO 00/60045, incorporated by reference. An example of a preferred catalyst is a transition metal complex of the MeN4Py ligand (N, bis (pyridin-2-yl-methyl) -1-, 1-bis (pyridin-2-yl) -1-aminoethane). Suitable bispidon catalyst materials and their action are described in WO 02/48301.

You can also use photo whiteners. 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 photobleaching agents can be selected from water-soluble phthalocyanine compounds, in particular metalated 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.

To reduce or avoid unwanted interactions with other liquid ingredients, the catalyst can be protected, for example by encapsulation.

Fragrance

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

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

It is even more preferable that the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and tissue retention. The deposition aid is preferably attached to the encapsulation by means of a covalent bond, entanglement or strong adsorption, preferably by a covalent bond or entanglement.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

Shading tinctures

Shading tincture can be used to improve the performance of the compositions used in the process of the present invention. The deposit of the shading dye on the fabric improves when used in the compositions of the invention and in accordance with the method of the invention. Preferred dyes are violet or blue. It is believed that the deposit on the fabrics of a low level of a dye 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 dyes are as described in WO09 / 153184.

The shading tincture can be used in the absence of a fluorescent agent, but it is especially preferred to use a shading tincture in combination with a fluorescent agent, for example in order 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 oxydisuccinic acid, methyl acid, benzene polycarboxylic acids and citric acid. Other examples are DEQUEST ™, organic phosphonate sequestering agents marketed by Thermphos and alkenohydroxy phosphonates. A particularly preferred sequestrant is HEDP sold by Thermphos as Dequest © 2010 and also known as 1-hydroxyethylidene -1,1-diphosphonic acid. Also suitable, but less preferred, are Dequest © 2066 (diethylenetriamine phosphonic acid of penta methylene or heptanedic DTPMP)

Other suitable structuring agents include high molecular weight polymers and copolymers known because they have structuring properties. For example, such materials include polyacrylic acid, polymaleic acid and suitable polyamine / polyamleic copolymers and their salts, 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.

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. The fiber of cftrico pulp is particularly preferred, especially if the lipase enzyme 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 alkaline liquid. Enzymes and bleaching catalysts are examples of such ingredients. Also perfumes, particularly microencapsulated perfumes ..

Packaging and dosage

The liquids can be packaged in unit doses in polymeric film adapted to be insoluble until added to the wash water. More preferably, the liquids are supplied in, preferably, multipurpose plastic packages with an upper or lower closure. A dosing system can be supplied with the package 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 front-loading automatic washing machine at a dose level of 20 ml. The low level of surfactant during washing is compensated by the presence of enzymes, stable dirt-releasing polymers and optional high-efficiency cleaning ingredients, such as EPEI. However, the invention is also suitable for more conventional dosage levels of approximately 35 ml. To obtain suitable liquids of this type, all that is needed is to add more water and possibly perfume to the 20 ml liquid type. The claimed soil release polymers are also stable in these more dilute compositions.

5

10

fifteen

twenty

25

30

35

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

Examples

In the following examples, the key to material abbreviations is as follows:

MPG is monopropylene glycol.

ASD is triethanolamine.

NI 7EO is C12-15 7EO ethoxylated alcohol non-ionic Neodol® 25-7 (ex Shell Chemicals).

LAS acid is C12-14 linear alkylbenzene sulfonic acid.

Prifac® 5908 is saturated lauric fatty acid ex Croda.

SLES 3EO is sodium lauryl ether sulfate with 3 moles EO.

Empigen® BB is an alkyl betama ex Huntsman (Coco dimethyl carbobetama).

EPEI is Sokalan HP20 - ethoxylated imine polyethylene cleaning polymer: PEI (600) 20EO ex

BASF

Perfume is oil free perfume.

SRP is dirt release polymers.

Prifac® 5908 is saturated lauric fatty acid ex Croda.

MEA is Monoethanolamine.

NaOH is 47% sodium hydroxide solution.

Dequest® 2066 is diethylenetriamine pentmethylene phosphonic acid (or Heptasodium DTPMP).

Dequest® 2010 is HEDP (1-hydroxyethylidene-1,1, -diphosphonic acid).

Lipex® is Lipex 100L ex Novozymes.

Carezyme® is a former Novozymes cellulase.

Stainzyme 12L is an amylase formulated for ex Novozymes liquids.

Mannaway is a mannaasa ex Novozymes.

All Tergo experiments have 2-prewash and a main wash. The BMD stain is applied after the second prewash. The load is 50:50 polyester fabric / cotton fabric in a mother water and clothing ratio of 25: 1. A 30-minute wash is carried out using an RPM of 100. AE ~ 6-10 is an excellent removal of the BMD stain; AE ~ 37 is equivalent to a performance in the absence of SRP; AE ~ 50 is equivalent to the stain before washing.

The hydrolytic stability of SRP (based on the cleaning performance of a DMO marker stain in polyester) of the composition given in Table 1 with the variation in pH due to the dose of sodium hydroxide is recorded in Table 2. A Smaller value for AE means better stain removal. Before washing the compositions they had been stored at 37 ° C for 8 weeks to give an indication of the resistance of the SRP to prolonged storage in the bottle.

Table 1-Composition 1-pH variation

 Raw material

 % (as 100%)

 Demim water

 up to 100%

 MPG

 twenty

 NaOH

 0

 TORCH

 2

 NI 7EO

 12.74

 LAS acid

 8.49

 Prifac 5908

 1.5

 SLES 3EO

 4.24

 They take BB

 1.5

 EPEI

 5.5

 SRP

 3.75

 Fragrance

 2.43

 PH adjustment hole

 10

Table 2- effect of storage pH on cleaning

 ASD%

 % NaOH pH AE

 2

 0.54 6.5 4

 2

 0.60 6.75 5.6

 2

 0.67 7 15.7

 3.5

 0.14 6.5 5.2

 3.6

 0.22 6.75 8.4

 3.5

 0.28 7 20.4

 4.09 (all ASD)

 0.98 6.5 17.9

 4.34 (all ASD)

 1.10 6.75 23

 4.66 (all ASD)

 1.25 7 28.3

 4.09

 0.05 6.75 19.6

 4.09

 0.14 7 27.2

At a pH of 6.5 and 6.75, good performance is observed with 2 and 3.5% by weight of ASD, which suggests acceptable SRP stability. Therefore, a target pH of 6.5 and the upper limit of pH less than 7.0 with up to 3.5% by weight of TEA are preferred for a composition as shown in Table 1. For a similar diluted composition with 5 water up to 1.5 times the volume the same pH range is required for stability and can be achieved with the correspondingly lower level of 2% by weight of ASD (i.e., pro rat).

Buffer control

A liquid detergent must be robust in pH in about 5% by weight of ingredients to allow manufacturing variability. To get that robustness it is necessary to include buffer in the Kquido. The buffers 10 used are TEA (pKa 7.8) and Prifac 5908 fatty acid (pKa unknown, since it is a mixture).

In WO09153184 3% of Prifac 5908 was used. In this level the fatty acid has a direct impact on the instability at low temperature, consequently, the level of fatty acid has been reduced to improve the stability at low temperature (in 20 ml of liquid of 1.71% and correspondingly 0.85% for 35 ml of compositions). The impact on the antifoam was checked and found to be acceptable. The impact of the reduction of Prifac 5908 on the buffer and the control of the pH with the 20 ml of compositions provided in Table 3 were also checked and considered acceptable (Table 4).

Table 3

 Raw material

 % (as 100%)

 Demim water

 up to 100%

 MPG

 twenty

 NaOH

 Up to target pH

 TORCH

 0 -3.5

 NI 7EO

 12.74

 LAS acid

 8.49

 Prifac 5908

 1.5

 SLES 3EO

 4.24

 They take BB

 1.5

 EPEI

 5.5

 SRP

 3.75

 Fragrance

 1.39

Table 4 - pH robustness control for the liquid in Table 3 depending on the TEA level

 Liquid from Table 3 with 1.5% of

 3.5% by weight of TEA 1% by weight of TEA pH 0% by weight of TEA pH

 Prifac 5908 +/- 5% by weight of ingredient verifier

 pH (target pH = 6.5) (target pH = 6.5) (target pH = 6.5)

 Diana

 6.51 6.54 6.50

 + 5% LAS acid

 6.11 6.05 5.77

 -5% LAS acid

 6.63 6.75 6.68

 + 5% ASD

 6.59 6.55 -

 -5% ASD

 6.28 6.34 -

 + 5% NaOH

 6.66 6.66 6.69

 -5% NaOH

 6.35 6.18 5.85

 + 5% of Prifac 5908

 6.38 6.47 6.22

 -5% of Prifac 5908

 6.5 6.47 6.33

 General pH range

 6.1 -6.7 6.0-6.8 5.7-6.7

The liquid in Table 3 has no pH control if there is no Prifac 5908 or ASD. Acceptable pH control can be achieved with 1.5% Prifac 5908 and at least 1% TEA. With 0% TEA the upper pH region is controlled, but the lower pH region is reduced to well below pH 6.0 which results in an unacceptable low temperature stability performance.

Low temperature stability

The two low temperature criteria are robustness at 5 ° C (with recovery at room temperature) for up to 12 weeks and freezing / thawing (with recovery at room temperature) for 1 week.

The level of fatty acid used is a key aspect of instability at low temperature and this is getting worse and worse at lower pH values (as the proportion of fatty acid and soap increases). The addition of ASD and MPG can overcome this instability if they are added to the required levels.

The starting point for the 20 ml of liquid composition based on SRP hydrolytic stability and pH control is a target pH of 6.5 with a minimum of 1% TEA and 1.5% Prifac 5908. The requirement of actual ASD is defined in Table 5 and the MPG requirement is defined in Table 6.

15 The preferred weight% of ASD is 3.5% and the preferred weight% of MPG is 20% for the liquid as defined in Table 1.

The starting point for a more diluted 35 ml composition is the same requirement for pH and 2% TEA. The level of MPG required for low temperature stability is shown in Table 7. The weight% of MPG required is 15% for the 35 ml of liquid.

20 Table 5 - Composition 1 liquid stability at low temperature with variable levels of ASD___________________

 % of ASD [with 1.5% of Prifac 5908 and 20% of MPG]

 Low temperature stability at pH 6.5 Low temperature stability at +/- 5% robustness tester

 3.5

 Approved Approved

 2

 Approved Approved

 one

 Not approved F / T Not tested

 0

 Not approved F / T Not tested

 F / T = freezing and defrosting

Table 6

 Raw material

 % (as 100%)

 Demim water

 up to 100%

 MPG

 LO CM O

 NaOH

 up to target pH

 TORCH

 3.5

 NI 7EO

 12.74

 LAS acid

 8.49

 Prifac 5908

 1.5

 SLES 3EO

 4.24

 They take BB

 1.5

 EPEI

 5.5

 SRP

 3.75

 Fragrance

 1.39

Table 7 - Temperature stability profile for the liquid in Table 6 as a function of pH and MPG level.

 MPG%

 Initial pH 1 day @ 5 ° C 1 week @ 5 ° C 1 week @ 5 ° C and recovery freezing and defrosting

 10

 6 Not approved Not approved Not approved Not approved Not approved

 10

 6.5 Not approved Not approved Not approved Not approved Not approved

 10

 7 Not approved Not approved Not approved Not approved Not approved

 10

 7.5 Not approved Not approved Not approved Not approved Not approved

 fifteen

 6 Approved Not approved Not approved Not approved Not approved

 fifteen

 6.5 Approved Approved Approved Approved Not Approved

 fifteen

 7 Approved Approved Approved Approved Not approved

 fifteen

 7.5 Approved Approved Approved Approved Not Approved

 twenty

 6 Approved Approved Approved Approved Approved

 twenty

 6.5 Approved Approved Approved Approved Approved

 twenty

 7 Approved Approved Approved Approved Approved

 twenty

 7.5 Approved Approved Approved Approved Approved

Table 8 - 35 ml of isotropic liquid

 Ingredient

 % (as 100%)

 Demim water

 up to 100%

 MPG

 or CM O

 NaOH

 up to target pH

 TORCH

 2.00

 NI 7EO

 7.28

 LAS acid

 4.85

 SLES 3EO

 2.42

 They take BB

 0.86

 Prifac 5908

 0.85

 EPEI

 3.10

 SRP

 2.10

 Fragrance

 1.39

 PH range

 6, 6.5, 7, 7.5, 8

Table 9 - Stability data for the composition of Table 8

 % MPG

 pH 6.0 pH 6.5 pH 7.0 pH 7.5 pH 8.0

 FT 5 RT FT 5 RT FT 5 RT FT 5 RT FT 5 RT

 twenty

 P R P P P P P P P P P P P P P

 fifteen

 P R P P P P P P P P P P P P P

 10

 F F P F F P P P P P P P P P P

 5

 F F F F F F F F P F P P F P P

 0

 F F F F F F F F F F F P F P P

 P = Approved F = Not approved R = Not approved at 5 ° C, but becomes isotropic on heating until RT

5

10

fifteen

Claims (16)

5 10 fifteen twenty 25 30 35 40 Four. Five fifty 1. A composition of isotonic Kquida detergent with a pH in the bottle in the range 6.0 to less than 7, the composition comprising, in addition to water: a) up to 60% by weight of detersive surfactant including at least 5% by weight of anionic sulphonate and / or sulfate surfactant comprising surfactant acid neutralized with one or more materials the pKa of whose conjugate acid (s) more than 2 units higher than the bottled pH of the liquid detergent composition b) at least 0.3% by weight of partially neutralized fatty acid with one or more materials, the pKa of whose conjugate acid (s) is more than 2 units higher than the pH in the liquid composition of the liquid Detergent - c) at least 1.0% by weight, preferably at least 1.8% by weight, of triethanolamine (TEA); Y d) at least 0.5% by weight of Dirt Release Polymers (SRP); provided that the composition is not one of the compositions (A), (B) or (C): (A) a composition consisting of 8.49% by weight of C12-14 linear alkylbenzene sulfonic acid, 4.24% by weight of sodium lauryl ether sulfate with 3 moles EO, 1.50% by weight of saturated lauric fatty acid Prifac® 5908, 12.74% by weight of ethoxylated C12-15 7EO non-ionic alcohol Neodol® 25-7, 0.15% by weight of NaOH solution (47%), 3.50% by weight of triethanolamine, 20.00% by weight of monopropylene glycol, 5.46% by weight of Sokalan HP20 ethoxylated imine polyethylene polymer (PEI (600) 20 EO), 3.55% by weight of Texcare SRN 170 Dirt-release polymer, 2.43% by weight of free perfume of oil, and water up to 100% by weight; (B) a composition consisting of 8.49% by weight of C12-14 linear alkylbenzene sulfonic acid, 4.24% by weight of sodium lauryl ether sulfate with 3 moles EO, 1.50% by weight of saturated lauric fatty acid Prifac® 5908, 12.74% by weight of ethoxylated C12-15 7EO non-ionic alcohol Neodol® 25-7, 0.15% by weight of NaOH solution (47%), 3.50% by weight of triethanolamine, 20.00% by weight of monopropylene glycol, 5.46% by weight of Sokalan HP20 ethoxylated imine polyethylene polymer (PEI (600) 20 EO), 3.55% by weight of Texcare SRN 170 Dirt release polymer, 1.63% by weight of Axis House RK 853 coconut hydroxamic acid, 2.43% by weight of oil-free perfume, and water up to 100% by weight; (C) a composition consisting of 8.49% by weight of C12-14 linear alkylbenzene sulfonic acid, 4.24% by weight of sodium lauryl ether sulfate with 3 moles EO, 1.50% by weight of saturated lauric fatty acid Prifac® 5908, 12.74% by weight of ethoxylated C12-15 7EO non-ionic alcohol Neodol® 25-7, 0.15% by weight of NaOH solution (47%), 3.50% by weight of triethanolamine, 20.00% by weight of monopropylene glycol, 5.46% by weight of Sokalan HP20 ethoxylated imine polyethylene polymer (PEI (600) 20 EO), 3.55% by weight of Texcare SRN 170 Dirt release polymer, 1.63% by weight of Axis House RK 852 coconut hydroxamate K + salt, 2.43% by weight of oil-free perfume, and water up to 100% by weight. 2. A composition according to claim 1 having a pH in the bottle of 6.3 to 6.7. 3. A composition according to any preceding claim in which the fatty acid is saturated. 4. A composition according to any preceding claim in which the fatty acid is used in an amount of 0.5 to 1.5% by weight. 5. A composition according to any preceding claim comprising up to 3.7% by weight of Triethanolamine (TEA), preferably 2.0 to 3.5% by weight. 6. A composition according to any preceding claim in which the one or more materials the pKa of which (s conjugate acid (s) is more than 2 units higher than the pH in the bottle of the liquid detergent composition comprises 0.08 to 0.25% by weight of NaOH and / or monoethanolamine (MEA), preferably 0.1 to 0.23% by weight. 7. A composition according to claim 6 wherein the one or more materials the pKa of whose conjugate acid (s) is more than 2 units higher than the pH in the bottle of the liquid detergent composition comprises 0.08 to 0.25% by weight monoethanolamine (MEA), preferably 0.1 to 0.23% by weight. 8. A composition according to any preceding claim in which the SRP has a substantive part of tissue formed by condensation of terephthalic acid ester and diol, preferably 1.2 propanediol, and also comprises a protected terminal hydrophilic part comprising repeated units of ethylene oxide protected with an alkyl group. 9. A composition according to any preceding claim wherein the liquid comprises a hydrotrope in an amount of at least 5% by weight, preferably at least 9% by weight and more preferably at least 14% by weight and much more preferably 1 , 2 propanediol (MPG). 10. A composition according to any preceding claim comprising at least 5% by weight of 5 ethoxylated imine poletylene (EPEI). 11. A composition according to any preceding claim wherein the anionic surfactant a) comprises at least 5% by weight of linear alkyl benzene sulphonate (LAS). 12. A composition according to any preceding claim comprising a zwitterionic surfactant, preferably carbobetama. 10 13. An isotonic liquid detergent composition packaged with a pH in the bottle in the range 6.0 to less that 7, the composition that includes, in addition to water: up to 60% by weight of detersive surfactant including at least 5% by weight of anionic sulphonate and / or sulphonate surfactant comprising surfactant acid neutralized with one or more materials the pKa of whose conjugate acid (s) is more than 2 units higher than the bottled pH of the liquid composition of 15 detergent. a) at least 0.3% by weight of partially neutralized fatty acid with one or more materials, the pKa of which conjugate acid (s) is more than 2 units higher than the pH in the liquid composition of the liquid Detergent b) at least 1.0% by weight, preferably at least 1.8% by weight, of Triethanolamine (TEA); Y 20 c) at least 0.5% by weight of soil release polymers (SRP). 14. An isotonic liquid detergent composition packaged according to claim 13 wherein the liquid is packaged as unit doses in polymeric film adapted to be insoluble until added to the wash water, or in which the liquids are supplied in packages multipurpose plastics with an upper or lower closure.