CN116583583A - Use and cleaning composition - Google Patents

Abstract

The present invention relates to combinations of rhamnolipid biosurfactants and amphoteric surfactants selected from the group consisting of betaines, glucosamides and sultaines for improved cleaning compositions containing primary alkyl sulfate surfactants The use of the product for cold cleaning performance at a temperature below 15°C, preferably below 12°C, more preferably 10°C and lower, wherein the primary alkyl sulfate is a C ₁₀ -C ₂₀ alkyl sulfate.

Description

Uses and Cleaning Compositions

technical field

The present invention relates to the use of combinations of amphoteric surfactants and biosurfactants for enhanced cleaning at low temperatures of primary alkyl sulfate anionic surfactants. The present invention also relates to cleaning compositions particularly suitable for cleaning at low temperatures, comprising primary alkyl sulfate surfactants, amphoteric surfactants and biosurfactants. .

Background of the invention

Primary alkyl sulfates are anionic surfactants useful for cleaning purposes. These surfactants are problematic with respect to their cleaning ability at low temperatures (eg below 15°C).

The present invention seeks to overcome the cleaning problems of primary alkyl sulfate surfactant cleansing compositions at low temperatures (eg, below 15°C).

Contents of the invention

We have found that by including a combination of an amphoteric surfactant and a biosurfactant, cleaning compositions containing primary alkyl sulphate surfactants are effective at temperatures below 15°C, preferably below 12°C, more preferably 10°C and below temperature has improved cleaning.

In a first aspect, the present invention relates to the combination of a rhamnolipid biosurfactant and an amphoteric surfactant selected from the group consisting of betaines, glucosamides and sultaines for improving primary alkyl sulfate-containing surfaces Use of an active cleaning composition for cold cleaning performance at temperatures below 15°C, preferably below 12°C, more preferably 10°C and below, wherein said primary alkyl sulfate is a C ₁₀ -C ₂₀ alkane base sulfate.

Preferably, in use, the ratio of primary alkyl sulfate surfactant to biosurfactant, preferably biosurfactant of microbial origin, most preferably rhamnolipid biosurfactant is from 8:1 to 1:10 , preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1; and the ratio of primary alkyl sulfate surfactant to amphoteric surfactant is 8: 1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1.

Preferably in use the cleaning composition is a fluid cleaning composition, more preferably an aqueous cleaning composition.

Preferably in use the cleaning composition comprises 1 to 30%, preferably 1 to 25%, more preferably 2.5 to 20%, most preferably 2.5 to 15% by weight of primary alkyl sulphate.

Preferably where used, the primary alkyl sulphate is sodium, potassium or ammonium C ₁₀ -C ₂₀ alkyl sulphate, even more preferably sodium C ₁₀ -C ₂₀ alkyl sulphate, most preferably sodium lauryl sulphate.

Preferably, in use, the cleaning composition comprises 1 to 10% by weight, more preferably 1 to 9% by weight, more preferably 1 to 8% by weight, most preferably 1.5 to 6% by weight rhamnolipid biosurfactant.

Preferably in use the rhamnolipid comprises at least 50% by weight of monorhamnolipids, more preferably at least 60% by weight of monorhamnolipids, even more preferably 70% by weight of monorhamnolipids, most preferably At least 80% by weight of monorhamnolipids, or wherein the rhamnolipids comprise at least 50% by weight of dirhamnolipids, more preferably at least 60% by weight of dirhamnolipids, even more preferably 70% by weight of dirhamnolipids Rhamnolipids, most preferably at least 80% by weight dirhamnolipids.

Preferably in use, the rhamnolipid is a dirhamnolipid of the formula: _{Rha2C8-12C8-12} , wherein the hydrocarbyl chain may _be saturated or unsaturated.

Preferably in use, the cleaning composition comprises 1 to 10% by weight, more preferably 1 to 9% by weight, more preferably 1 to 8% by weight, most preferably 1.5 to 6% by weight of and amphoteric surfactants of the sultaine class.

Preferably, in use, the amphoteric surfactant is selected from cocamidopropyl betaine and lauryl hydroxysultaine, most preferably the amphoteric surfactant is lauryl hydroxysultaine.

Preferably in use, the composition is a household care cleaning composition.

Preferably, in use, the composition further comprises one or more enzymes selected from the group consisting of lipases, proteases, amylases, cellulases and mixtures thereof.

Preferably in use the detergent composition has a pH of 4 to 11, more preferably 5 to 10, even more preferably 5 to 9 when dissolved in demineralized water at 4g/L at 293K.

Preferably, in use, the composition is a cleaning composition comprising:

a) 1 to 30% by weight of primary alkyl sulfate surfactants;

b) 1 to 10% by weight of an amphoteric surfactant selected from the group consisting of betaines, glucamides and sultaines; and

c) 1 to 10% by weight of a rhamnolipid biosurfactant;

Wherein the ratio of primary alkyl sulfate surfactant to biosurfactant is 8:1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1; and

Wherein the ratio of primary alkyl sulfate surfactant to amphoteric surfactant is 8:1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1;

Wherein said primary alkyl sulfate is C ₁₀ -C ₂₀ alkyl sulfate.

Description of drawings

Figure 1 shows the beneficial effect of a combination of a rhamnolipid biosurfactant and an amphoteric surfactant to improve the cold cleaning performance at 10°C of a cleaning composition containing a primary alkyl sulfate surfactant. The performance of PAS degrades at such low temperatures.

Detailed ways

Combination of amphoteric surfactants selected from betaines, glucosamides and sultaines with rhamnolipid biosurfactants for enhanced cleaning of primary alkyl sulfate anionic surfactants at low temperatures . Low temperature as used herein refers to temperatures below 15°C, preferably below 12°C, more preferably 10°C and lower.

Preferably in use the ratio of primary alkyl sulfate surfactant to rhamnolipid biosurfactant is from 8:1 to 1:10, preferably from 7:1 to 1:5, more preferably from 6:1 to 1 :2, even more preferably from 6:1 to 1:1; and the ratio of primary alkyl sulfate surfactant to amphoteric surfactant is from 8:1 to 1:10, preferably from 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1.

Use of amphoteric surfactants selected from betaines, glucosamides and sultaines in combination with rhamnolipid biosurfactants to enhance cleaning at low temperatures of primary alkyl sulfate anionic surfactants It may suitably be shown as a preferred composition according to the invention as described on the following pages.

The use of the present invention may be demonstrated by a cleaning composition comprising:

a) 1 to 30% by weight of primary alkyl sulfate surfactants;

b) 1 to 10% by weight of an amphoteric surfactant selected from the group consisting of betaines, glucamides and sultaines; and,

c) 1 to 10% by weight of a rhamnolipid biosurfactant;

Wherein the ratio of primary alkyl sulfate surfactant to biosurfactant is 8:1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1; and

Wherein the ratio of primary alkyl sulfate surfactant to amphoteric surfactant is 8:1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1;

Wherein said primary alkyl sulfate is C ₁₀ -C ₂₀ alkyl sulfate.

primary alkyl sulfate

The cleaning composition comprises 1 to 30% by weight, preferably 1 to 25% by weight, preferably 2.5 to 20% by weight, most preferably 2.5 to 15% by weight of primary alkyl sulphate.

Primary alkyl sulfates are C ₁₀ -C ₂₀ alkyl sulfates, preferably lauryl sulfate.

The primary alkyl sulfate is preferably in the form of a counterion, more preferably a sodium, potassium or ammonium ion.

Examples of preferred materials include sodium C ₁₀ -C ₂₀ alkyl sulfates, most preferably sodium lauryl sulfate.

Primary alkyl sulfates do not include alkoxylated sulfates, ie the term primary alkyl sulfates does not include primary ether sulfates.

The ratio of primary alkyl sulfate surfactant to rhamnolipid biosurfactant is 8:1-1:10, preferably 7:1-1:5, more preferably 6:1-1:2, even more preferably 6:1-1:1.

The ratio of primary alkyl sulfate surfactant to amphoteric surfactant is 8:1-1:10, preferably 7:1-1:5, more preferably 6:1-1:2, even more preferably 6:1- 1:1.

The ratio of primary alkyl sulfate surfactant to amphoteric surfactant and the ratio of primary alkyl sulfate surfactant to rhamnolipid biosurfactant may each individually or together also preferably be from 5:1 to 1 :1, preferably 4:1 to 1:1, more preferably 3:1 to 1:1, most preferably 2.75:1 to 1:1, or even 2.5 to 1:1.

biosurfactant

Preferably, the rhamnolipid biosurfactant is present in the formulation at 1 to 9% by weight, more preferably 1 to 8% by weight, most preferably 1.5 to 6% by weight.

Biosurfactants are rhamnolipids. These are a class of glycolipids. They consist of rhamnose combined with beta-hydroxy fatty acids. Rhamnose is sugar. Fatty acids are ubiquitous in animals and plants.

Rhamnolipids are discussed by E. Deziel et al. in Applied Microbiology and Biotechnology (2010) 86:1323-1336. Rhamnolipids were produced by Evonik, Stepan, Glycosurf, AGAE Technologies and UrumqiUnite Bio-Technology Co., Ltd. Rhamnolipids can be produced by strains of the bacterium Pseudomonas Aeruginosa. There are two main groups of rhamnolipids: monorhamnolipids and dirhamnolipids.

Monorhamnolipids have a single rhamnose sugar ring. A typical monorhamnolipid produced by Pseudomonas aeruginosa is L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (RhaC ₁₀ C ₁₀ ). It may be referred to as Rha-C ₁₀ -C ₁₀ , having the formula C ₂₆ H ₄₈ O ₉ . Monorhamnolipids have a single rhamnose sugar ring.

The IUPAC name is 3-[3-[(2R,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxydecanoyloxy] capric acid.

Dirhamnolipids have two rhamnose sugar rings. A typical dirhamnolipid is L-rhamnosyl-L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (Rha2C ₁₀ C ₁₀ ). It may be referred to as Rha-Rha-C- ₁₀ -C- ₁₀ , having the formula C ₃₂ H ₅₈ O ₁₃ .

The IUPAC name is 3-[3-[4,5-dihydroxy-6-methyl-3-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxa Cyclohex-2-yl]oxydecanoyloxy]decanoic acid.

In practice, a variety of other minor components with different combinations of alkyl chain lengths are present in combination with the more common rhamnolipids described above, depending on the carbon source and bacterial strain. The ratio of monorhamnolipid and dirhamnolipid can be controlled by the production method. Some bacteria only produce mono-rhamnolipids, see US 5767090: Example 1, some enzymes can convert mono-rhamnolipids into di-rhamnolipids.

In various publications, monorhamnolipids have the label Rha-, which can be abbreviated Rh or RL2. Similarly, dirhamnolipids have the label Rha-Rha or Rh-Rh- or RL1. For historical reasons, "rhamnolipid 2" is a monorhamnolipid and "rhamnolipid 1" is a dirhamnolipid. This leads to some ambiguity in the use of "RL1" and "RL2" in the literature.

In this patent specification we use the terms mono- and di-rhamnolipids to avoid this possible confusion. However, if an abbreviation is used, R1 is a mono-rhamnolipid and R2 is a di-rhamnolipid. See the introduction to US 4814272 for more information on term confusion in the prior art.

The following rhamnolipids have been detected as produced by the following bacteria: (C12:1, C14:1 represent fatty acyl chains with double bonds).

Rhamnolipids (monorhamnolipids) produced by Pseudomonas aeruginosa:

Rha-C8-C10, Rha-C10-C8, Rha-C-10-C10, Rha-C10-C12, Rha-C10-C12:1, Rha-C12-C10, Rha-C12:1-C10.

Rhamnolipids (dirhamnolipids) produced by Pseudomonas aeruginosa:

Rha-Rha-C8-C10, Rha-Rha-C8-C12:1, Rha-Rha-C10-C8, Rha-Rha-C10-C10, Rha-Rha-C10-C12:1, Rha-Rha-C- 10-C-12, Rha-Rha-C-12-C-10, Rha-Rha-C-12:1-C-12, Rha-Rha-C-10-C14:1.

Rhamnolipids produced by Pseudomonas aeruginosa (not identified as mono- or di-rhamnolipids):

C8-C8, C8-C10, C10-C8, C8-C12:1, C12:1-C8, C10-C10, C12-C10, C12:1-C10 C12-C12, C12:1-C12, C14-C10 , C14:1-C10, C14-C14.

Rhamnolipids produced by P. chlorophis (monorhamnolipids only):

Rha-C10-C8, Rha-C10-C10, Rha-C12-C10, Rha-C12:1-C10, Rha-C12-C12, Rha-C12:1-C12, Rha-C14-C10.Rha-C- 14:1-C-10.

Rhamnolipids produced by Burkholderera pseudomallei (dirhamnolipids only):

Rha-Rha-C14-C14.

Rhamnolipids (dirhamnolipids only) produced by Burkholderera plantarii (Pseudomonas):

Rha-Rha-C14-C14.

There are over 100 archived strains of P. aeruginosa at the American Type Culture Collection (ATCC). There are also many strains available only to commercial rhamnolipid manufacturers. In addition, there may be thousands of strains isolated by various research institutions worldwide. Some work has classified them into groups. Each strain has different characteristics, including how much rhamnolipid is produced, which type of rhamnolipid is produced, what it metabolizes, and the conditions under which it is grown. Only a small subset of strains has been extensively studied.

Through evaluation and selection, Pseudomonas aeruginosa can be isolated to produce rhamnolipids at higher concentrations and more efficiently. It is also possible to select strains that produce fewer by-products and metabolize different feedstocks or pollutants. This production is greatly influenced by the environment in which the bacteria grow.

A typical dirhamnolipid _{is L -} rhamnosyl-L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (Rha ₂ C ₁₀ C ₁₀ ).

In practice, a variety of other minor components with different combinations of alkyl chain lengths are present in combination with the more common rhamnolipids above, depending on the carbon source and bacterial strain. The ratio of monorhamnolipid and dirhamnolipid can be controlled by the production method. Some bacteria only produce mono-rhamnolipids, see US 5767090: Example 1, some enzymes can convert mono-rhamnolipids into di-rhamnolipids.

Preferably, the rhamnolipids are selected from:

- Rhamnolipids (monorhamnolipids) produced by Pseudomonas aeruginosa:

Rha-C8-C10, Rha-C10-C8, Rha-C10-C10, Rha-C10-C12, Rha-C10-C12:1, Rha-C12-C10, Rha-C12:1-C10.

- Rhamnolipids produced by Pseudomonas chloropins (only monorhamnolipids):

Rha-C10-C8, Rha-C10-C10, Rha-C12-C10, Rha-C12:1-C10, Rha-C12-C12, Rha-C12:1-C12, Rha-C14-C10, Rha-C14: 1-C10.

- Monorhamnolipids can also be produced from Pseudomonas putida (P. putida) by introducing the genes rhIA and rhIB from Pseudomonas aeruginosa [Cha et al. Bioresour Technol. 2008.99(7):2192-9].

- Rhamnolipids (dirhamnolipids) produced by Pseudomonas aeruginosa:

Rha-Rha-C8-C10, Rha-Rha-C8-C12:1, Rha-Rha-C10-C8, Rha-Rha-C10-C10, Rha-Rha-C10-C12:1, Rha-Rha-C10- C12, Rha-Rha-C12-C10, Rha-Rha-C12:1-C12, Rha-Rha-C10-C14:1

- Rhamnolipids produced by Burkholderia pseudomallei (dirhamnolipids only):

Rha-Rha-C14-C14.

- Rhamnolipids (dirhamnolipids only) produced by Burkholderia planta (Pseudomonas):

Rha-Rha-C14-C14.

- Rhamnolipids produced by Pseudomonas aeruginosa, which were not originally identified as mono- or di-rhamnolipids:

C8-C8, C8-C10, C10-C8, C8-C12:1, C12:1-C8, C10-C10, C12-C10, C12:1-C10, C12-C12, C12:1-C12, C14- C10, C14: 1-C10, C14-C14.

Most preferably, the rhamnolipid is L-rhamnosyl-β-hydroxydecanoyl-β-hydroxydecanoate (RhaC ₁₀ C ₁₀ having the formula C ₂₆ H ₄₈ O _{9 )} produced by Pseudomonas aeruginosa ).

Preferably, the rhamnolipid comprises at least 50% by weight monorhamnolipid, more preferably at least 60% by weight monorhamnolipid, even more preferably 70% by weight monorhamnolipid, most preferably at least 80% by weight monorhamnolipid rhamnolipid; or, wherein the rhamnolipid comprises at least 50% by weight of dirhamnolipid, more preferably at least 60% by weight of dirhamnolipid, even more preferably 70% by weight of dirhamnolipid, most preferably Preferably at least 80% by weight dirhamnolipid.

Preferably, the rhamnolipid is a dirhamnolipid of the formula: Rha2C _8-12 C _8-12 . Preferred alkyl chain lengths are C ₈ -C ₁₂ . The hydrocarbyl chain can be saturated or unsaturated.

amphoteric surfactant

The surfactant combination comprises from 1 to 10% by weight of an amphoteric (also known as zwitterionic) surfactant.

Preferably, the cleaning composition comprises 1 to 9%, preferably 1 to 8%, most preferably 1.5 to 6% by weight of amphoteric surfactant.

The amphoteric surfactant is selected from the group consisting of betaines, glucamides and sultaines, preferably selected from cocamidopropyl betaine and lauryl hydroxy sultaine, most preferably the amphoteric surfactant is lauryl Hydroxysultaine.

cleaning composition

The compositions are cleaning compositions, which are useful for cleaning substrates, such as surfaces, including for household and personal care purposes. The composition is preferably a fluid cleaning composition, more preferably an aqueous cleaning composition.

Preferably, the cleaning composition is a home care composition.

Such compositions are useful, for example, in hand dishwashing to clean substrates such as tableware, crockery, glassware, plastics and metal.

Such compositions can be used, for example, for laundry purposes, to wash textiles.

Preferably, the cleaning composition is a laundry detergent composition, more preferably a liquid laundry detergent or a powder detergent.

pH

Preferably, the detergent composition has a pH of 4 to 11, more preferably 5 to 10, even more preferably 5 to 9 when dissolved in demineralized water at 4g/L, 293K.

Preferably, when a liquid laundry detergent, the laundry detergent composition has a pH of 6 to 11, more preferably 6 to 9 when dissolved in demineralized water at 4g/L, 293K.

additional surfactant

Additional surfactants may be present in the composition.

Preferably, the cleaning composition comprises 0 to 20% by weight, more preferably 0 to 10% by weight, of additional surfactants.

These are preferably selected from anionic and nonionic surfactants.

Generally, the nonionic and anionic surfactants of the surfactant system can be selected from Schwartz & Perry's "Surface Active Agents" Vol.1, Interscience 1949, Schwartz, Perry & Berch's Vol.2, Interscience 1958, current edition published by Manufacturing Confectioners Company "McCutcheon's Emulsifiers and Detergents" or "Tenside-Taschenbuch", H. Stache, 2nd Edn, Carl Hauser Verlag, 1981. Preferably, the surfactants used are saturated.

Preferred nonionic detergent compounds that can be used include compounds having hydrophobic groups and reactive hydrogen atoms (e.g. aliphatic alcohols, acids, amides) with alkylene oxides (especially ethylene oxide alone or with propylene oxide together with ethylene oxide) reaction product. Particular nonionic detergent compounds are condensation products of aliphatic linear or branched primary or secondary alcohols with ethylene oxide, typically 5-40EO, preferably 7EO-9EO.

Preferred anionic detergent compounds that can be used are generally the water-soluble alkali metal salts of organic sulfuric and sulfonic acids having alkyl groups having from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of the higher acyl group. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl C ₁₀ -C ₂₀ benzene sulfonates, especially linear secondary alkyl C ₁₀ -C ₁₅ sodium benzene sulfonates; and sodium alkyl glyceryl ether sulfates, especially are those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. A preferred anionic detergent compound is sodium _C11 - _C15 alkylbenzene sulphonate. Also applicable are surfactants such as those described in EP-A-328177 (Unilever) which exhibit resistance to salting out, the alkyl polyglycoside surfactants described in EP-A-070074 and the alkyl monoglycosides.

Preferred surfactant systems are mixtures of anionic and nonionic detergent actives.

Preferably, the additional surfactants are predominantly anionic surfactants by weight.

cleaning booster

Cleaning enhancers may preferably be present in the composition.

The composition preferably comprises from 0.5% to 15% by weight, more preferably from 0.75% to 15% by weight, even more preferably from 1% to 12% by weight, most preferably from 1.5% to 10% by weight of a cleaning boost An agent selected from the group consisting of anti-redeposition polymers; soil release polymers; alkoxylated polycarboxylates as described in WO2019/008036 and WO2019/007636; and mixtures thereof.

Anti-redeposition polymer

Preferred anti-redeposition polymers include alkoxylated polyamines.

Preferred alkoxylated polyamines include alkoxylated polyethyleneimines and/or alkoxylated polypropyleneimines. Polyamines can be linear or branched. It can be branched to the point that it is a dendrimer. Alkoxylation can generally be ethoxylated or propoxylated, or a mixture of both. When the nitrogen atom is alkoxylated, the preferred average degree of alkoxylation is 10-30, preferably 15-25. Preferred materials are ethoxylated polyethyleneimines with an average degree of ethoxylation of 10-30, preferably 15-25, wherein the nitrogen atoms are ethoxylated.

soil release polymer

Preferably, the soil release polymer is a polyester soil release polymer.

Preferred soil release polymers include those described in WO2014/029479 and WO2016/005338.

Preferably, the polyester based soil release polymer is a polyester according to the following formula (I):

in

R ¹ and R ² are independently of each other X-(OC ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m , wherein X is C _1-4 alkyl and preferably methyl, -(OC ₂ H ₄ ) group Groups and -(OC ₃ H ₆ ) groups are arranged block by block, and the blocks composed of -(OC ₃ H ₆ ) groups are combined with COO groups or are HO-(C ₃ H ₆ ), and preferably independently of each other is X-(OC ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m ,

n is based on a molar average of 12-120, preferably 40-50,

m is a molar average based on 1-10, preferably 1-7, and

a is based on the molar average of 4-9.

Preferably the polyester is provided as a reactive blend comprising:

A) 45 to 55% by weight of reactive blends of one or more polyesters according to the following formula (I)

in

R ¹ and R ² are independently of each other X-(OC ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m , wherein X is C _1-4 alkyl and preferably methyl, -(OC ₂ H ₄ ) group Groups and -(OC ₃ H ₆ ) groups are arranged block by block, and the blocks composed of -(OC ₃ H ₆ ) groups are combined with COO groups or are HO-(C ₃ H ₆ ), and preferably independently of each other is X-(OC ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m ,

n is based on a molar average of 12-120, preferably 40-50,

m is a molar average based on 1-10, preferably 1-7, and

a is a molar average based on 4 to 9, and

B) 10% to 30% by weight of the reactive blend of one or more alcohols selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol alcohols, 1,3-butanediol, 1,4-butanediol, and butyl glycol, and

C) 24% to 42% water by weight of the active blend.

Alkoxylated Polycarboxylates

Alkoxylated polycarboxylates can be obtained by first making an aromatic polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably three or four carboxylic acid units or anhydrides derived therefrom An aromatic polycarboxylic acid, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic anhydride, most preferably trimellitic anhydride, is reacted with an alcohol alkoxylate, And in a second step the resulting product is reacted with an alcohol or a mixture of alcohols, preferably with a C16/C18 alcohol.

further ingredients

The cleaning composition may comprise any of these further preferred ingredients.

One or more of these further ingredients are particularly useful if the cleaning composition is a home care composition, especially if it is used for hand dishwashing or laundry purposes.

Builder or complexing agent

Builder materials may be selected from 1) calcium chelator materials, 2) precipitating materials, 3) calcium ion exchange materials and 4) mixtures thereof.

Examples of calcium chelating agent builders include alkali metal polyphosphates such as sodium tripolyphosphate and organic chelating agents such as ethylenediaminetetraacetic acid.

Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.

Examples of calcium ion exchange builder materials include various types of water insoluble crystalline or amorphous aluminosilicates of which zeolites are the most well known representatives such as zeolite A, zeolite B (also known as zeolite P), zeolite C, Zeolite X, Zeolite Y and P-type zeolites as described in EP-A-0384070.

The composition may also contain 0-65% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or hereinafter other builders mentioned. Many builders are also bleach stabilizers due to their ability to complex metal ions.

Zeolites and carbonates (including bicarbonates and sesquicarbonates) are preferred builders.

The compositions may contain crystalline aluminosilicates as builders, preferably alkali metal aluminosilicates, more preferably sodium aluminosilicates. This is usually present at a level of less than 15% by weight. Aluminosilicates are materials with the general formula:

0.8-1.5M ₂₀ .Al ₂ O ₃ .0.8-6SiO ₂

wherein M is a monovalent cation, preferably sodium. These materials contain some bound water and need to have a calcium ion exchange capacity of at least 50 mgCaO/g. Preferred sodium aluminosilicates contain 1.5-3.5 _SiO2 units in the above formula. They can be readily prepared by reaction between sodium silicates and sodium aluminates, as well described in the literature. The ratio of surfactant to aluminosilicate (when present) is preferably greater than 5:2, more preferably greater than 3:1.

As an alternative or in addition to aluminosilicate builders, phosphate builders can be used. In the art, the term "phosphate" includes diphosphate, triphosphate and phosphonate species. Other forms of builders include silicates, eg soluble silicates, metasilicates, layered silicates (eg SKS-6 from Hoechst).

Preferably, the laundry detergent formulation comprises less than 1% by weight phosphate. If builders are included, preferably the laundry detergent formulation is carbonate built.

fluorescent agent

The composition preferably comprises a fluorescer (optical brightener).

Fluorescent agents are well known, and many such fluorescent agents are commercially available. Typically, these fluorescers are supplied and used in the form of their alkali metal salts, eg sodium salts. The total amount of one or more fluorescent agents used in the composition is generally from 0.005 to 2% by weight, more preferably from 0.01 to 0.1% by weight. Preferred classes of fluorescent agents are: distyryl biphenyl compounds such as Tinopal (trademark) CBS-X, diamine distyryl disulfonic acid compounds such as Tinopal DMS pure Xtra and Blankophor (trademark) HRH, and pyrazoline Compounds such as Blankophor SN. Preferred fluorescent 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}stilbene-2-2' disodium sulfonate, 4, 4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2' disodium sulfonate, and 4 ,4'-Bis(2-sulfostyrene)biphenyl disodium.

Preferably, the aqueous solution used in the method has a fluorescer present. When the fluorescer is present in the aqueous solution used in the process, it is preferably in the range of 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.

dye

The composition preferably comprises a dye. Dyes are discussed in K. Hunger (ed). Industrial Dyes: Chemistry, Properties, Applications (Weinheim: Wiley-VCH 2003). Organic dyes are listed in the Color Index (Society of Dyers and Colourists and the American Association of TextileChemists and Colorists).

Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane.

Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charge or are uncharged. Azine dyes preferably carry a net anionic or cationic charge.

Preferred non-shading dyes are selected from blue dyes, most preferably anthraquinone dyes bearing sulfonate groups and triphenylmethane dyes bearing sulfonate groups. Preferred compounds are Acid Blue 80, Acid Blue 1, Acid Blue 3; Acid Blue 5, Acid Blue 7, Acid Blue 9, Acid Blue 11, Acid Blue 13, Acid Blue 15, Acid Blue 17, Acid Blue 24, Acid Blue 34, acid blue 38, acid blue 75, acid blue 83, acid blue 91, acid blue 97, acid blue 93, acid blue 93:1, acid blue 97, acid blue 100, acid blue 103, acid blue 104, acid blue 108, acid blue 109, acid blue 110 and acid blue 213. When dissolved, the particles with non-hueing dyes provide an attractive color to the wash liquor.

Blue or violet hueing dyes are most preferred. During the wash or rinse step of the laundering process, hueing dyes are deposited onto fabrics, providing the fabrics with a visible shade. In this regard, the dye imparts a blue or purple color to white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white cloth used in this test is a piece of bleached non-mercerized textile cotton.

Hue dyes are discussed in WO 2005/003274, WO 2006/032327 (Unilever), WO 2006/032397 (Unilever), WO 2006/045275 (Unilever), WO 2006/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO 2009/132870 (Unilever), WO 2009/141173 (Unilever), WO 2010/099997 (Unilever), WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO 2008 /087497(P&G), WO 2011/011799(P&G), WO 2012/054820(P&G), WO2013/142495(P&G) and WO 2013/151970(P&G).

Mixtures of hueing dyes may be used.

The hueing dye chromophore is most preferably selected from monoazo, disazo, anthraquinone and azine.

The monoazo dyes preferably contain heterocycles and are most preferably thiophene dyes. The monoazo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO 2013/142495 and WO 2008/087497.

The most preferred hueing dyes are selected from direct violet 9, direct violet 99, direct violet 35, solvent violet 13, disperse violet 28, dyes of the following structures:

spices

Preferably, the composition includes fragrance. Perfume is preferably in the range of 0.001 to 3% by weight, most preferably 0.1 to 1% by weight. Many examples of suitable fragrances are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications, and the OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

It is not uncommon for multiple fragrance components to be present in formulations. In the compositions of the invention it is envisaged that four or more, preferably five or more, more preferably six or more or even seven or more different perfume components are present.

In the perfume mixture, preferably 15-25% by weight are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from the group consisting of citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

It is preferred that the laundry treatment composition is free of peroxygen bleaches such as sodium percarbonate, sodium perborate and peracids.

polymer

The composition may contain one or more additional polymers. Examples are carboxymethylcellulose, poly(ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Polymers that prevent dye deposition, such as poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), may be present in the formulation.

enzyme

When carrying out the methods of the present invention, one or more enzymes are preferably present in the cleaning compositions of the present invention.

Preferably, the content of each enzyme in the composition of the invention is from 0.0001% to 0.1% by weight of protein.

Particularly contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases, or mixtures thereof.

Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include those from the genus Humicola (synonym Thermomyces), for example from H. lanuginosa (Thermomyces lanuginosa) (T.lanuginosus)) (as described in EP 258068 and EP 305216) or from Humicola insolens (H.insolens) (as described in WO96/13580), Pseudomonas lipase, for example from Pseudomonas Pseudomonas (P.alcaligenes) or pseudoalcaligenes (P.pseudoalcaligenes) (EP 218 272), Pseudomonas cepacia (P.cepacia) (EP 331376), Pseudomonas stutzeri (P .stutzeri) (GB 1,372,034), Pseudomonas fluorescens (P.fluorescens), Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), Pseudomonas wisconsin (P wisconsinensis) (WO 96/12012), Bacillus lipase, e.g. from Bacillus subtilis (B.subtilis) (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), Bacillus stearothermophilus ( B. stearothermophilus) (JP 64/744992) or B. pumilus (WO91/16422).

Other examples are lipase variants, for example in WO 92/05249, WO 94/01541, EP 407 225, EP 260105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/ 14783, those described in WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063.

Preferred commercially available lipases include Lipolase ^™ and Lipolase Ultra ^™ , Lipex ^™ and lipoclean ^™ (Novozymes A/S).

The method of the invention may be performed in the presence of a phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme active on phospholipids.

Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids at the outer (sn-1) and middle (sn-2) positions and phosphorylated at the third position; phosphoric acid in turn can Esterification with amino alcohols. Phospholipases are enzymes involved in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipase A1 and A2, which hydrolyze a fatty acyl group (at the sn-1 and sn-2 positions, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which Can hydrolyze remaining fatty acyl groups in lysophospholipids.

Phospholipase C and phospholipase D (phosphodiesterases) release diacylglycerol or phosphatidic acid, respectively.

Enzymes and photobleaches may show some interaction and should be chosen such that the interaction is not negative. Some negative interactions can be avoided by encapsulating one or the other of the enzyme or photobleach within the product and/or by other sequestration.

Suitable proteases include those of animal, vegetable or microbial origin. Preference is given to microbial origin. Chemically modified or protein engineered 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 proteases include Alcalase ^™ , Savinase ^™ , Primase ^™ , Duralase ^™ , Dyrazym ^™ , Esperase ^™ , Everlase ^™ , Polarzyme ^™ and Kannase ^™ , (Novozymes A/S), Maxatase ^™ , Maxacal ^™ , Maxapem ^™ , Properase ^™ , Purafect ^™ , PurafectOxP ^™ , FN2 ^™ and FN3 ^™ (Genencor International Inc.).

The method of the invention may be carried out in the presence of cutinases classified in EC 3.1.1.74. The cutinase used according to the invention may be of any origin.

Preferably the cutinase is of microbial origin, especially of bacterial, fungal or yeast origin.

Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin.

Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example, a special strain of Bacillus licheniformis described in more detail in GB 1296839, or disclosed in WO 95/026397 or WO 00/060060 Bacillus strains. Commercially available amylases are Duramyl ^™ , Termamyl ^™ , Termamyl Ultra ^™ , Natalase ^™ , Stainzyme ^™ , Fungamyl ^™ and BAN ^™ (Novozymes A/S), Rapidase ^™ and Purastar ^™ (from Genencor International Inc.).

Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example from US 4,435,307, US 5,648,263, US 5,691,178 , US5,776,757, WO 89/09259, WO 96/029397 and WO 98/012307, Humicola insolens, Thielavia terrestris, Myceliophthorathermophila and Oxysporum Fungal cellulase produced by Fusarium oxysporum.

Commercially available cellulases include Celluzyme ^™ , Carezyme ^™ , Celluclean ^™ , Endolase ^™ , Renozyme (Novozymes A/S), Clazinase ^™ and Puradax HA ^™ (Genencor International Inc.) and KAC-500(B) ^™ (Kao Corporation ).

Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin.

Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, such as from C. cinereus, and variants thereof, such as WO 93/24618, WO 95/10602 and described in WO 98/15257.

Commercially available peroxidases include Guardzyme ^™ and Novozym ^™ 51004 (Novozymes A/S).

Other suitable enzymes are discussed in WO 2009/087524, WO 2009/090576, WO 2009/107091, WO 2009/111258 and WO 2009/148983.

enzyme stabilizer

Any enzymes present in the composition may be stabilized using conventional stabilizers, for example polyols such as propylene glycol or glycerol, sugars or sugar alcohols, lactic acid, boric acid or boric acid derivatives such as aromatic borates, or phenylboronic acid derivatives such as 4- formylphenylboronic acid, and compositions may be formulated as described in, for example, WO 92/19709 and WO 92/19708.

Alkyl encompasses branched, cyclic and straight alkyl chains when the alkyl is sufficiently long to form a branched or cyclic chain. The alkyl group is preferably linear or branched, most preferably linear.

As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean at least one, or one or more, unless otherwise stated.

The invention will be further described by the following non-limiting examples.

Example

Example 1

Various solutions were prepared containing either a single surfactant system or a mixture of PAS, HS and rhamnolipid.

materials used

PAS = Sodium Lauryl Sulfate (SLS)-Stepanol WA-Extra HP-Stepan

HS-Lauryl Hydroxysultaine (HS)-Mackam LHS-GN-Solvay

R2-rhamnolipid-Rewoferm-Evonik

clean measurement

Tergotometer evaluation to evaluate the cleaning performance of the formulations under the following conditions

·Temperature -10°C or 25°C

Liquid:cloth ratio-100:1

· Water Type - Demineralized

Stain - CS46b (Fried Fat with Purple Dye on Textile Cotton)

·Washing time - 30 minutes

· Stirring rate -100rpm

· Ballast Type - Textile Cotton

· Ballast mass - 10g

• Formulation dose - 2 g/L except for the PAS:HS:R2 formulation (8:4.5:4.5), where the dose was reduced to 1.65 g/L to balance active levels throughout the test.

1 rinse in 1L demineralized water

Details of the formulations tested (14% active each except the PAS:HS:R2 formulation (which was prepared at 17%)):

Element Level (wt.%) PAS 14 PAS:HS 11:3 PAS: R2 11:3 PAS:HS:R2 8:4.5:4.5

Table 1. Surfactant Mixtures of Compositions Tested

PAS, PAS:HS and PAS:R2 are 14% by weight surfactant active compositions fed at 2 g/L. PAS:HS:R2 is a 17% by weight surfactant active composition fed at 1.65 g/L. This was done to balance the in-use surfactant activity levels between all tested compositions.

PAS - 14% solution of Stepanol WA-Extra HP in demineralized water

PAS: HS - 11% Stepanol WA - Extra HP, 3% Mackam LHS - GN in demineralized water

PAS: R2 - 11% Stepanol WA-Extra HP in demineralized water, 3% Rewoferm

PAS:HS:R2 - 8% Stepanol WA-Extra HP, 4.5% Mackam LHS-GN, 4.5% Rewoferm in demineralized water

The cleaning results are shown in Figure 1. Cleaning performance was measured by ΔSRI, which measures the stain removal performance of the compositions in Table 1. ΔSRI is the improvement in stain removal relative to treatment of stained articles using the composition.

Figure 1 shows the beneficial effect of a combination of a rhamnolipid biosurfactant and an amphoteric surfactant to improve the cold cleaning performance at 10°C of a cleaning composition containing a primary alkyl sulfate surfactant. The performance of PAS drops at such low temperatures (10°C) compared to 25°C. While the inclusion of biosurfactants (rhamnolipids) or amphoteric surfactants (while keeping the overall surfactant levels the same) slightly improved cleaning, only combinations of biosurfactants (rhamnolipids) and amphoteric surfactants Together improve the cold cleaning (10°C) performance of the PAS surfactants to levels above that seen for PAS alone at 25°C.

These results indicate that the combination of biosurfactant and amphoteric surfactant improves the cold cleaning performance at 10°C of cleaning compositions containing primary alkyl sulfate surfactants.

Claims (13)

1. Combination of rhamnolipid biosurfactant and amphoteric surfactant selected from betaines, glucosamides and sultaines for improving cleaning compositions containing primary alkyl sulfate surfactants Use for cold cleaning performance at temperatures below 15°C, preferably below 12°C, more preferably 10°C and lower, wherein the primary alkyl sulfate is a C ₁₀ -C ₂₀ alkyl sulfate. 2. purposes as claimed in claim 1, wherein the ratio of primary alkyl sulfate surfactant and rhamnolipid biosurfactant is 8:1 to 1:10, preferred 7:1 to 1:5, more Preferably from 6:1 to 1:2, even more preferably from 6:1 to 1:1; and the ratio of primary alkyl sulfate surfactant to amphoteric surfactant is from 8:1 to 1:10, preferably from 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1. 3. Use according to claim 1 or claim 2, wherein the cleaning composition is a fluid cleaning composition, more preferably an aqueous cleaning composition. 4. Use according to any one of the preceding claims, wherein the cleaning composition comprises 1 to 30% by weight, preferably 1 to 25% by weight, more preferably 2.5 to 20% by weight, most preferably 2.5 to 15% by weight of Primary Alkyl Sulfate. 5. Use according to any one of the preceding claims, wherein the primary alkyl sulphate is sodium, potassium or ammonium C ₁₀ -C ₂₀ alkyl sulphate, even more preferably sodium C ₁₀ -C ₂₀ alkyl sulphate, Sodium lauryl sulfate is most preferred. 6. Use according to any one of the preceding claims, wherein the cleaning composition comprises 1 to 10% by weight, more preferably 1 to 9% by weight, more preferably 1 to 8% by weight, most preferably 1.5 to 6% by weight rhamnolipid biosurfactants. 7. The use according to any one of the preceding claims, wherein the rhamnolipid comprises at least 50% by weight of monorhamnolipid, more preferably at least 60% by weight of monorhamnolipid, even more preferably 70% by weight. % by weight of monorhamnolipid, most preferably at least 80% by weight of monorhamnolipid, or wherein said rhamnolipid comprises at least 50% by weight of dirhamnolipid, more preferably at least 60% by weight of dirhamnolipid A rhamnolipid, even more preferably 70% by weight dirhamnolipid, most preferably at least 80% by weight dirhamnolipid. 8. Use according to any one of the preceding claims, wherein the cleaning composition comprises 1 to 10% by weight, more preferably 1 to 9% by weight, more preferably 1 to 8% by weight, most preferably 1.5 to 6% by weight amphoteric surfactants. 9. Use according to any one of the preceding claims, wherein the amphoteric surfactant is selected from cocamidopropyl betaine and lauryl hydroxy sultaine, most preferably said amphoteric surfactant is lauryl Hydroxysultaine. 10. Use according to any one of the preceding claims, wherein the composition is a household care cleaning composition. 11. Use according to any one of the preceding claims, wherein the composition further comprises one or more enzymes selected from the group consisting of lipases, proteases, amylases, cellulases and mixtures thereof. 12. The use according to any one of the preceding claims, wherein the composition has a value of 4 to 11, more preferably 5 to 10, even more preferably 5 to 10 when dissolved in demineralized water at 4 g/L, 293K. 9 pH. 13. Use according to any one of the preceding claims, wherein the composition is a cleaning composition comprising: a) 1 to 30% by weight of primary alkyl sulfate surfactants; b) 1 to 10% by weight of an amphoteric surfactant selected from the group consisting of betaines, glucamides and sultaines; and c) 1 to 10% by weight of a rhamnolipid biosurfactant; Wherein the ratio of primary alkyl sulfate surfactant to biosurfactant is 8:1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1; and Wherein the ratio of primary alkyl sulfate surfactant to amphoteric surfactant is 8:1 to 1:10, preferably 7:1 to 1:5, more preferably 6:1 to 1:2, even more preferably 6:1 to 1:1; Wherein said primary alkyl sulfate is C ₁₀ -C ₂₀ alkyl sulfate.