CN116583583A

CN116583583A - Use and cleaning composition

Info

Publication number: CN116583583A
Application number: CN202180084977.4A
Authority: CN
Inventors: N·J·布朗比尔; R·卡拉蒂; J·赛弗特; P·S·史蒂文森
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2020-12-17
Filing date: 2021-12-10
Publication date: 2023-08-11
Also published as: WO2022128786A1; EP4263771A1

Abstract

The present invention relates to the use of a combination of a rhamnolipid biosurfactant and an amphoteric surfactant selected from the group consisting of betaines, glucamides and sulfobetaines for improving the cold cleaning performance of a cleaning composition containing a primary alkyl sulfate surfactant at temperatures below 15 ℃, preferably below 12 ℃, more preferably 10 ℃ and below, wherein the primary alkyl sulfate is C ₁₀ ‑C ₂₀ Alkyl sulfate.

Description

Use and cleaning composition

Technical Field

The present invention relates to the use of a combination of an amphoteric surfactant and a biosurfactant for enhancing the cleaning of primary alkyl sulfate anionic surfactants at low temperatures. The invention also relates to cleaning compositions comprising primary alkyl sulfate surfactants, amphoteric surfactants, and biosurfactants that are particularly suitable for cleaning at low temperatures. .

Background

Primary alkyl sulfates are anionic surfactants that can be used for cleaning purposes. These surfactants have problems with respect to cleaning ability at low temperatures (e.g., below 15 ℃).

The present invention seeks to overcome the cleaning problem of primary alkyl sulfate surfactant cleaning compositions at low temperatures (e.g. below 15 ℃).

Disclosure of Invention

We have found that by including a combination of amphoteric and biosurfactants, cleaning compositions containing primary alkyl sulfate surfactants have improved cleaning at temperatures below 15 ℃, preferably below 12 ℃, more preferably 10 ℃ and below.

In a first aspect, the present invention relates to the use of a combination of a rhamnolipid biosurfactant and an amphoteric surfactant selected from the group consisting of betaines, glucamides and sulfobetaines for improving the cold cleaning performance of a cleaning composition comprising a primary alkyl sulfate surfactant at a temperature below 15 ℃, preferably below 12 ℃, more preferably below 10 ℃ and below, wherein the primary alkyl sulfate is C ₁₀ -C ₂₀ Alkyl sulfate.

Preferably, in use, the ratio of primary alkyl sulfate surfactant to biosurfactant, preferably biosurfactant of microbial origin, most preferably rhamnolipid 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 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 from 6:1 to 1:2, even more preferably from 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 from 1 to 30 wt%, preferably from 1 to 25 wt%, more preferably from 2.5 to 20 wt%, most preferably from 2.5 to 15 wt% primary alkyl sulphate.

Preferably in use, the primary alkyl sulfate is C ₁₀ -C ₂₀ Sodium, potassium or ammonium alkyl sulphates, even more preferably C ₁₀ -C ₂₀ Sodium alkyl sulfate, most preferably sodium lauryl sulfate.

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

Preferably in use the rhamnolipid comprises at least 50 wt% of a mono rhamnolipid, more preferably at least 60 wt% of a mono rhamnolipid, even more preferably 70 wt% of a mono rhamnolipid, most preferably at least 80 wt% of a mono rhamnolipid, or wherein the rhamnolipid comprises at least 50 wt% of a di rhamnolipid, more preferably at least 60 wt% of a di rhamnolipid, even more preferably 70 wt% of a di rhamnolipid, most preferably at least 80 wt% of a di rhamnolipid.

Preferably in use, the rhamnolipid is a di-rhamnolipid of the formula: rha2C _8-12 C _8-12 Wherein the hydrocarbyl chain may be saturated or unsaturated.

Preferably, in use, the cleaning composition comprises from 1 to 10 wt%, more preferably from 1 to 9 wt%, more preferably from 1 to 8 wt%, most preferably from 1.5 to 6 wt% of an amphoteric surfactant selected from betaines, glucamides and sulfobetaines.

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

Preferably, in use, the composition is a home 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 from 4 to 11, more preferably from 5 to 10, even more preferably from 5 to 9 when dissolved in demineralised water at 4g/L, 293K.

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

a) 1 to 30 wt% primary alkyl sulfate surfactant;

b) 1 to 10 wt% of an amphoteric surfactant selected from betaines, glucamides, and sulfobetaines; and

c) 1 to 10 wt% 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 is also provided with

Wherein 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 from 6:1 to 1:2, even more preferably from 6:1 to 1:1;

wherein the primary alkyl sulfate is C ₁₀ -C ₂₀ Alkyl sulfate.

Drawings

Figure 1 shows the beneficial effect of a combination of rhamnolipid biosurfactants and amphoteric surfactants to improve the cold cleaning performance of cleaning compositions containing primary alkyl sulfate surfactants at 10 ℃. The PAS performance is degraded at such low temperatures.

Detailed Description

Amphoteric surfactants selected from betaines, glucamides and sulfobetaines are used in combination with rhamnolipid biosurfactants to enhance cleaning of primary alkyl sulfate anionic surfactants at low temperatures. Low temperature as used herein refers to temperatures below 15 ℃, preferably below 12 ℃, more preferably 10 ℃ and below.

Preferably, in use, the ratio of primary alkyl sulfate surfactant to rhamnolipid 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 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 from 6:1 to 1:2, even more preferably from 6:1 to 1:1.

The use of a combination of an amphoteric surfactant selected from betaines, glucamides and sulfobetaines with a rhamnolipid biosurfactant to enhance cleaning of primary alkyl sulfate anionic surfactants at low temperatures may suitably be shown as a preferred composition according to the present invention as described in the following pages.

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

a) 1 to 30 wt% primary alkyl sulfate surfactant;

b) 1 to 10 wt% of an amphoteric surfactant selected from betaines, glucamides, and sulfobetaines; and, a step of, in the first embodiment,

c) 1 to 10 wt% of a rhamnolipid biosurfactant;

wherein the primary alkyl sulfate is C ₁₀ -C ₂₀ Alkyl sulfate.

Primary alkyl sulfates

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

The primary alkyl sulfate being C ₁₀ -C ₂₀ Alkyl sulfates, preferably lauryl sulfate.

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

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

The primary alkyl sulfate does not include an alkoxylated sulfate, i.e., the term primary alkyl sulfate does not include a primary ether sulfate.

The ratio of primary alkyl sulfate surfactant to rhamnolipid 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.

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 from 6:1 to 1:2, even more preferably from 6:1 to 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, alone or together, also preferably be 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 wt%, more preferably 1 to 8 wt%, most preferably 1.5 to 6 wt%.

The biosurfactant is rhamnolipid. These are a class of glycolipids. They consist of rhamnose in combination with beta-hydroxy fatty acids. Rhamnose is a 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 are produced by Evonik, stepan, glycosurf, AGAE Technologies and Urumqi Unite Bio-Technology co. Rhamnolipids can be produced by a strain of the bacterium pseudomonas aeruginosa (Pseudomonas Aeruginosa). There are two main groups of rhamnolipids: mono-and di-rhamnolipids.

The rhamnolipid has a monosaccharide sugar ring. A typical monose produced by Pseudomonas aeruginosa is L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (RhaC) ₁₀ C ₁₀ ). It can be called Rha-C ₁₀ -C ₁₀ Has the following advantages ofC (C) ₂₆ H ₄₈ O ₉ . The rhamnolipid has a monosaccharide sugar ring.

IUPAC name 3- [3- [ (2 r,3r,4r,5r,6 s) -3,4, 5-trihydroxy-6-methyloxahex-2-yl ] oxy decanoyloxy ] decanoic acid.

The rhamnolipid has two rhamnose sugar rings. Typical rhamnolipids are L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (Rha 2C) ₁₀ C ₁₀ ). It can be called Rha-Rha-C- ₁₀ -C- ₁₀ Having a formula C ₃₂ H ₅₈ O ₁₃ 。

IUPAC name is 3- [3- [4, 5-dihydroxy-6-methyl-3- (3, 4, 5-trihydroxy-6-methyloxycyclohex-2-yl) oxy-oxacyclohex-2-yl ] oxy decanoyloxy ] decanoic acid.

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

In various publications, the monorhamnolipids have the label Rha-, which may be abbreviated as Rh or RL2. Similarly, the rhamnolipids have the label Rha-Rha or Rh-Rh-or RL1. For historical reasons, "rhamnolipid 2" is a monose glucolipid and "rhamnolipid 1" is a di-rhamnolipid. 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 abbreviations are used, R1 is mono-rhamnolipid and R2 is di-rhamnolipid. For more information on term confusion in the prior art see the introduction of US 4814272.

The following rhamnolipids have been tested as produced by the following bacteria: (C12:1, C14:1 represents a fatty acyl chain having a double bond).

Rhamnolipids (monosrhamnolipids) 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 (ditrhamnolipids) 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 (not identified as mono-or di-rhamnolipids) produced by pseudomonas aeruginosa:

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 (mono rhamnolipids only) produced by pseudomonas aeruginosa (p.chlorographis):

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 (ditolyl only) produced by burkholderia melioides (Burkholdera pseudomallei):

Rha-Rha-C14-C14。

rhamnolipids (ditrhamnolipids only) produced by burkholderia plantarii (Burkholdera plantarii) (pseudomonas):

Rha-Rha-C14-C14。

over 100 archived strains of P.aeruginosa exist in 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 research institutions worldwide. Some work has classified them into groups. Each strain has different characteristics including how much rhamnolipid is produced, what type of rhamnolipid is produced, what it metabolizes, and the conditions under which it grows. Only a small fraction of strains are widely studied.

By evaluation and selection, pseudomonas aeruginosa can be isolated to produce rhamnolipids at higher concentrations and more efficiently. Strains that produce fewer byproducts and metabolize different feedstocks or contaminants can also be selected. This production is greatly affected by the environment in which the bacteria grow.

Typical rhamnolipids are L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (of formula C ₃₂ H ₅₈ O ₁₃ Rha of (C) ₂ C ₁₀ C ₁₀ )。

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

Preferably, the rhamnolipid is selected from:

rhamnolipids (monosrhamnolipids) 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 aeruginosa (mono rhamnolipids 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-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 Bioresource technology.2008.99 (7): 2192-9].

Rhamnolipids (ditrhamnolipids) 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 (ditolyl only) produced by burkholderia meliotidis:

Rha-Rha-C14-C14。

rhamnolipids (ditolyl only) produced by burkholderia plantarii (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 produced by pseudomonas aeruginosa (having formula C ₂₆ H ₄₈ O ₉ RhaC of (C) ₁₀ C ₁₀ )。

Preferably, the rhamnolipid comprises at least 50 wt% of a mono rhamnolipid, more preferably at least 60 wt% of a mono rhamnolipid, even more preferably 70 wt% of a mono rhamnolipid, most preferably at least 80 wt% of a mono rhamnolipid; alternatively, wherein the rhamnolipid comprises at least 50 wt% of a rhamnolipid, more preferably at least 60 wt% of a rhamnolipid, even more preferably 70 wt% of a rhamnolipid, most preferably at least 80 wt% of a rhamnolipid.

Preferably, the rhamnolipid is a ditrhamnolipid of the formula: rha2C _8-12 C _8-12 . Preferred alkyl chain lengths are C ₈ -C ₁₂ . The hydrocarbyl chain may be saturated or unsaturated.

Amphoteric surfactants

The surfactant combination comprises 1 to 10 wt.% of an amphoteric (also referred to as zwitterionic) surfactant.

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

The amphoteric surfactant is selected from betaines, glucamides and sulfobetaines, preferably selected from cocoamidopropyl betaine and lauryl hydroxysulfobetaine, most preferably the amphoteric surfactant is lauryl hydroxysulfobetaine.

Cleaning composition

The composition is a cleaning composition that can be used to clean a substrate, such as a surface, including for home 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 dishes, crockery, glassware, plastics and metals.

Such compositions are useful, for example, for laundry purposes to launder 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 from 4 to 11, more preferably from 5 to 10, even more preferably from 5 to 9 when dissolved in demineralised water at 4g/L, 293K.

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

Additional surfactant

Additional surfactants may be present in the composition.

Preferably, the cleaning composition comprises from 0 to 20 wt%, more preferably from 0 to 10 wt% of an additional surfactant.

These are preferably selected from anionic and nonionic surfactants.

In general, the nonionic and anionic surfactants of the surfactant system may be selected from "Surface Active Agents" Vol.1, interscience1949, schwartz, perry & Berch, vol.2, interscience 1958, the current versions "McCutcheon's Emulsifiers and Detergents" or "Tenside-Taschenbuch", H.Stache,2nd Edn,Carl Hauser Verlag,1981, published by Manufacturing Confectioners Company. Preferably, the surfactant used is saturated.

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

Preferred anionic detergent compounds which may be used are generally water-soluble alkali metal salts of organic sulfuric and sulfonic acids having alkyl groups containing from about 8 to about 22 carbon atoms, the term alkyl being used for the alkyl portion including higher acyl groups. Examples of suitable synthetic anionic detergent compounds are alkyl C ₁₀ -C ₂₀ Sodium and potassium benzenesulfonates, in particular linear secondary alkyl C ₁₀ -C ₁₅ Sodium benzenesulfonate; and sodium alkyl glyceryl ether sulphates, particularly those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. Preferred anionic detergent compounds are C ₁₁ -C ₁₅ Sodium alkylbenzenesulfonate. Also useful are surfactants such as those described in EP-A-328177 (Unilever), which exhibit resistance to salting out, alkyl polyglycoside surfactants and alkyl monoglycosides described in EP-A-070074.

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

Preferably, the additional surfactant is mainly an anionic surfactant by weight.

Cleaning enhancer

The cleaning enhancing agent may preferably be present in the composition.

The composition preferably comprises from 0.5 wt% to 15 wt%, more preferably from 0.75 wt% to 15 wt%, even more preferably from 1 wt% to 12 wt%, most preferably from 1.5 wt% to 10 wt% of a cleaning booster selected from anti-redeposition polymers; a soil release polymer; alkoxylated polycarboxylic esters as described in WO2019/008036 and WO 2019/007536; and mixtures thereof.

Anti-redeposition polymers

Preferred anti-redeposition polymers include alkoxylated polyamines.

Preferred alkoxylated polyamines include alkoxylated polyethylenimines and/or alkoxylated polypropylenimines. The polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer. Alkoxylation may generally be ethoxylation or propoxylation, or a mixture of both. When the nitrogen atom is alkoxylated, the preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25. A preferred material is an ethoxylated polyethylenimine having an average degree of ethoxylation of from 10 to 30, preferably from 15 to 25, wherein the nitrogen atoms are ethoxylated.

Soil release polymers

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

Preferred soil release polymers include those described in WO2014/029479 and WO 2016/005338.

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

wherein the method comprises the steps of

R ¹ And R is ² X- (OC) independently of one another ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m Wherein X is C _1-4 Alkyl and preferably methyl, - (OC) ₂ H ₄ ) Radicals and- (OC) ₃ H ₆ ) The groups being arranged block by block and consisting of- (OC) ₃ H ₆ ) The blocks consisting of groups being bound to COO groups or HO- (C) ₃ H ₆ ) And are preferably X- (OC) independently of each other ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m ，

n is an average number of moles, based on 12 to 120, preferably 40 to 50,

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

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

Preferably, the polyester is provided as a reactive blend comprising:

a) 45 to 55% by weight of a reactive blend of one or more polyesters according to the formula (I)

Wherein the method comprises the steps of

R ¹ And R is ² X- (OC) independently of one another ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m Wherein X is C _1-4 Alkyl and preferably methyl, - (OC) ₂ H ₄ ) Radicals and- (OC) ₃ H ₆ ) The groups being arranged in block-by-block fashion and consisting of- (OC) ₃ H ₆ ) The blocks consisting of groups being bound to COO groups or HO- (C) ₃ H ₆ ) And are preferably X- (OC) independently of one another ₂ H ₄ ) _n -(OC ₃ H ₆ ) _m ，

n is an average number of moles, based on 12 to 120, preferably 40 to 50,

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

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

b) From 10% to 30% by weight of the active blend of one or more alcohols selected from the group consisting of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, and butylethylene glycol, and

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

Alkoxylated polycarboxylic esters

The alkoxylated polycarboxylic esters can be obtained as follows: an aromatic polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or anhydrides derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or anhydrides derived therefrom, even more preferably trimellitic acid or anhydride, most preferably trimellitic anhydride, is first reacted with an alcohol alkoxylate and the resulting product is reacted in a second step with an alcohol or alcohol mixture, preferably 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 for hand dishwashing or laundry purposes.

Builder or complexing agent

The builder material may be selected from 1) calcium chelating materials, 2) precipitation materials, 3) calcium ion exchange materials, and 4) mixtures thereof.

Examples of calcium chelator builders include alkali metal polyphosphates such as sodium tripolyphosphate and organic chelators such as ethylenediamine tetraacetic acid.

Examples of precipitated 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 zeolite as described in EP-a-0384070.

The composition may also contain 0-65% of a builder or complexing agent, such as ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, alkyl-or alkenyl succinic acids, nitrilotriacetic acid or other builders mentioned below. 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 composition may contain a crystalline aluminosilicate as builder, preferably an alkali metal aluminosilicate, more preferably sodium aluminosilicate. This is typically present at a level of less than 15% by weight. Aluminosilicates are materials having the general formula:

0.8-1.5M ₂₀ .Al ₂ O ₃ .0.8-6SiO ₂

wherein the method comprises the steps ofM is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50mg CaO/g. Preferred sodium aluminosilicates contain 1.5 to 3.5 SiO's in the above formula ₂ A unit. They can be readily prepared by the reaction between sodium silicate and sodium aluminate, as fully described in the literature. The ratio of surfactant to aluminosilicate (when present) is preferably greater than 5:2, more preferably greater than 3:1.

Alternatively or in addition to aluminosilicate builders, phosphate builders can be used. In the art, the term "phosphate" includes the di-, tri-and phosphonate species. Other forms of builder include silicates, such as soluble silicate, metasilicate, layered silicate (e.g. SKS-6 from Hoechst).

Preferably, the laundry detergent formulation comprises less than 1 wt% phosphate. If a builder is included, it is preferred that the laundry detergent formulation is carbonate builder.

Fluorescent agent

The composition preferably comprises a fluorescent agent (optical brightener).

Fluorescent agents are well known and many such fluorescent agents are commercially available. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts, e.g., sodium salts. The total amount of one or more fluorescent agents used in the composition is typically 0.005 to 2 wt%, more preferably 0.01 to 0.1 wt%. Preferred classes of fluorescent agents are: stilbene biphenyl compounds, such as Tinopal (trade mark) CBS-X, diamine stilbenedisulfonic acid compounds, such as Tinopal DMS pure Xtra and Blankophor (trade mark) HRH, and pyrazoline compounds, such as Blankophor SN. Preferred fluorescers are: sodium 2- (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d ] triazoles, disodium 4,4' -bis { [ (4-anilino-6- (N-methyl-N-2 hydroxyethyl) amino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, disodium 4,4' -bis { [ (4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.

Preferably, the aqueous solution used in the method has a fluorescent agent present. When present in the aqueous solution used in the method, the fluorescent agent is preferably in the range of 0.0001g/l to 0.1g/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). The organic dyes are listed in the color index (Society of Dyers and Colourists and the American Association of Textile Chemists 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. Upon dissolution, the particles with the non-hueing dye provide an attractive color to the wash liquor.

Blue or violet hueing dyes are most preferred. During the washing or rinsing step of the washing process, hueing dye is deposited onto the fabric, thereby providing a visible hue to the fabric. In this regard, the dye imparts a blue or violet color to the white cloth at a hue angle of 240 to 345, more preferably 260 to 320, and most preferably 270 to 300. The white cloth used in this test was a bleached non-mercerized woven cotton sheet.

Hueing 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), WO 2013/142495 (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 dye preferably contains a heterocyclic ring, and most preferably is a thiophene dye. The monoazo dye is preferably alkoxylated and is preferably uncharged or anionically charged at ph=7. Alkoxylated thiophene dyes are discussed in WO 2013/142495 and WO 2008/087497.

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 structure:

spice

Preferably, the composition comprises a perfume. The perfume is preferably in the range of 0.001 to 3 wt%, most preferably 0.1 to 1 wt%. Many examples of suitable fragrances are provided in CTFA (Cosmetic, toiletry and Fragrance Association) 1992International Buyers Guide published by CFTA Publications and OPD 1993Chemicals Buyers Directory 80th Annual Edition published by Schnell Publishing co.

It is common for a variety of perfume components to be present in the formulation. In the compositions of the present invention, it is envisaged that there are four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.

Preferably 15-25 wt% of the perfume mixture is top notes. The top note is defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80[1955 ]). Preferred top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose ethers and cis-3-hexanol.

It is preferred that the laundry treatment composition is free of peroxygen bleach, for example sodium percarbonate, sodium perborate and peracid.

Polymer

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

Enzymes

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

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

Enzymes of particular concern 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 lipases from Humicola (synonymous with Thermomyces), for example from Humicola lanuginosa (H.lanuginosa) (Thermomyces lanuginosus) (T.lanuginosus)) (as described in EP 258068 and EP 305116) or from Humicola insolens (H.insolens) (as described in WO 96/13580), pseudomonas lipases, such as from Pseudomonas alcaligenes or Pseudomonas alcaligenes (P.pseudoalcaligenes) (EP 218 272), pseudomonas cepacia (P.cepacia) (EP 331 376), pseudomonas stutzeri (P.stutzeri) (GB 1,372,034), pseudomonas fluorescens (P.fluoroscens), pseudomonas sp strain SD 705 (WO 95/06720 and WO 96/27002), pseudomonas Wisconsii (P.wisconsiensis) (WO 96/12012), bacillus lipases, such as from Bacillus subtilis (B.subtilis) (Dartois et al (1993), biochemica et Biophysica Acta,1131,253-360), bacillus stearothermophilus (B.stearothermophilus) (JP 64/744992) or Bacillus pumilus (B.pumilus) (WO 91/16422).

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, WO 00/60063.

Preferred commercially available lipases include Lipolase ^TM And Lipolase Ultra ^TM 、Lipex ^TM And lipoclear ^TM (Novozymes A/S)。

The process of the invention may be carried out in the presence of a phospholipase classified as EC3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme active towards phospholipids.

Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in the outer (sn-1) and middle (sn-2) positions and phosphorylated in the third position; the phosphoric acid can in turn be esterified with an amino alcohol. Phospholipase is an enzyme involved in phospholipid hydrolysis. Several types of phospholipase activity can be distinguished, including phospholipase A1 and A2 that hydrolyzes one fatty acyl group (at sn-1 and sn-2 positions, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze fatty acyl groups remaining in lysophospholipid.

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

The enzyme and photo-bleach may exhibit some interactions and should be selected such that the interactions are not negative. By encapsulating one or the other of the enzyme or photo-bleach within the product and/or by other isolation, some negative interactions may be avoided.

Suitable proteases include those of animal, plant or microbial origin. Preferably of 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 commercial proteases include Alcalase ^TM 、Savinase ^TM 、Primase ^TM 、Duralase ^TM 、Dyrazym ^TM 、Esperase ^TM 、Everlase ^TM 、Polarzyme ^TM And Kannase ^TM 、(Novozymes A/S)、Maxatase ^TM 、Maxacal ^TM 、Maxapem ^TM 、Properase ^TM 、Purafect ^TM 、Purafect OxP ^TM 、FN2 ^TM And FN3 ^TM (Genencor International Inc.)。

The process of the invention may be carried out in the presence of a cutinase 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, in particular of bacterial, fungal or yeast origin.

Suitable amylases (α and/or β) include those of bacterial or fungal origin.

Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus (Bacillus), for example, the particular strain of Bacillus licheniformis described in more detail in GB 1296839, or the Bacillus strains disclosed in WO 95/026397 or WO 00/060060. The commercially available amylase is Duramyl ^TM 、Termamyl ^TM 、Termamyl Ultra ^TM 、Natalase ^TM 、Stainzyme ^TM 、Fungamyl ^TM And BAN ^TM (Novozymes A/S)、Rapidase ^TM And Purastar ^TM (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 the genera Bacillus, pseudomonas, humicola, fusarium, thielavia, acremonium, such as fungal cellulases produced by U.S. Pat. No. 4,435,307, U.S. Pat. No. 5,648,263, U.S. Pat. No. 5,691,178, U.S. Pat. No. 5,776,757, WO 89/09259, WO 96/029397 and WO 98/0123307, humicola insolens (Humicola insolens), thielavia terrestris (Thielavia terrestris), myceliophthora thermophila (Myceliophthora thermophila) and Fusarium oxysporum (Fusarium oxysporum).

Commercially available cellulases include Celluzyme ^TM 、Carezyme ^TM 、Celluclean ^TM 、Endolase ^TM 、Renozyme(Novozymes A/S)、Clazinase ^TM And Puradax HA ^TM (Genencor International Inc.) and KAC-500 (B) ^TM (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 (Coprinus), for example from Coprinus cinereus (C.cinereus), and variants thereof, as described in WO 93/24618, WO 95/10602 and WO 98/15257.

Commercially available peroxidases include Guardzyme ^TM And Novozym ^TM 51004(Novozymes A/S)。

Other enzymes suitable for use are discussed in WO 2009/087524, WO 2009/090576, WO 2009/107091, WO2009/111258 and WO 2009/148983.

Enzyme stabilizer

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

Alkyl groups encompass branched, cyclic, and straight alkyl chains when the alkyl groups are long enough to form branched or cyclic chains. The alkyl group is preferably linear or branched, most preferably linear.

The indefinite articles "a" or "an" and their corresponding definite articles "the" as used herein mean at least one, or one or more, unless otherwise specified.

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

Examples

Example 1

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

The materials used

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

HS-lauryl Hydroxysulfobetaine (HS) -Mackam LHS-GN-Solvay

R2-rhamnolipid-Rewoferm-Evonik

Clean measurement

Detergent scale (terglometer) evaluation to evaluate the cleaning performance of the formulations under the following conditions

Temperature of-10℃or 25 DEG C

Liquid to cloth ratio-100:1

Water type-demineralized

stain-CS 46b (frying fat with purple dye on textile Cotton cloth)

Washing time-30 minutes

Stirring Rate-100 rpm

Ballast type-textile cotton

Ballast mass-10 g

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

1 rinse in 1L demineralized water

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

composition of the components	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 the tested compositions

PAS, PAS HS and PAS R2 are 14 wt.% of a surfactant active composition, which is fed at 2 g/L. PAS HS R2 is 17 wt% of the surfactant active composition, which is fed at 1.65 g/L. This was done to balance surfactant activity levels in use across all tested compositions.

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

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

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

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

The cleaning results are shown in FIG. 1. The cleaning performance was measured by Δsri, which measures the soil release performance of the compositions in table 1.Δsri is an improvement in stain removal relative to the treatment of stained articles with the composition.

Figure 1 shows the beneficial effect of a combination of rhamnolipid biosurfactants and amphoteric surfactants to improve the cold cleaning performance of cleaning compositions containing primary alkyl sulfate surfactants at 10 ℃. The PAS performance is degraded at such low temperature (10 ℃) compared to 25 ℃. Although inclusion of biosurfactants (rhamnolipids) or amphoteric surfactants (while maintaining the overall surfactant level the same) slightly improves cleaning, the combination of biosurfactants (rhamnolipids) and amphoteric surfactants alone improve the cold cleaning (10 ℃) performance of PAS surfactants to a level above that seen for PAS alone at 25 ℃.

These results demonstrate that the combination of biosurfactants and amphoteric surfactants improves the cold cleaning performance of cleaning compositions containing primary alkyl sulfate surfactants at 10 ℃.

Claims

1. Use of a combination of a rhamnolipid biosurfactant and an amphoteric surfactant selected from the group consisting of betaines, glucamides and sulfobetaines for improving the cold cleaning performance of a cleaning composition containing a primary alkyl sulfate surfactant at temperatures below 15 ℃, preferably below 12 ℃, more preferably 10 ℃ and below, wherein the primary alkyl sulfate is C ₁₀ -C ₂₀ Alkyl sulfate.

2. The use according to claim 1, wherein the ratio of primary alkyl sulfate surfactant to rhamnolipid 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 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 from 6:1 to 1:2, even more preferably from 6:1 to 1:1.

3. The use according to claim 1 or claim 2, wherein the cleaning composition is a fluid cleaning composition, more preferably an aqueous cleaning composition.

4. The use according to any of the preceding claims, wherein the cleaning composition comprises from 1 to 30 wt%, preferably from 1 to 25 wt%, more preferably from 2.5 to 20 wt%, most preferably from 2.5 to 15 wt% primary alkyl sulphate.

5. The use according to any one of the preceding claims, wherein the primary alkyl sulfate is C ₁₀ -C ₂₀ Sodium, potassium or ammonium alkyl sulphates, even more preferably C ₁₀ -C ₂₀ Sodium alkyl sulfate, most preferably sodium lauryl sulfate.

6. The use according to any preceding claim, wherein the cleaning composition comprises from 1 to 10 wt%, more preferably from 1 to 9 wt%, more preferably from 1 to 8 wt%, most preferably from 1.5 to 6 wt% of rhamnolipid biosurfactant.

7. The use according to any of the preceding claims, wherein the rhamnolipid comprises at least 50 wt% of a mono-rhamnolipid, more preferably at least 60 wt% of a mono-rhamnolipid, even more preferably 70 wt% of a mono-rhamnolipid, most preferably at least 80 wt% of a mono-rhamnolipid, or wherein the rhamnolipid comprises at least 50 wt% of a di-rhamnolipid, more preferably at least 60 wt% of a di-rhamnolipid, even more preferably 70 wt% of a di-rhamnolipid, most preferably at least 80 wt% of a di-rhamnolipid.

8. Use according to any one of the preceding claims, wherein the cleaning composition comprises from 1 to 10% by weight, more preferably from 1 to 9% by weight, more preferably from 1 to 8% by weight, most preferably from 1.5 to 6% by weight of the amphoteric surfactant.

9. Use according to any one of the preceding claims, wherein the amphoteric surfactant is selected from cocamidopropyl betaine and lauryl hydroxysulfobetaine, most preferably the amphoteric surfactant is lauryl hydroxysulfobetaine.

10. The use according to any preceding claim, wherein the composition is a home care cleaning composition.

11. The use according to any 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. Use according to any one of the preceding claims, wherein the composition has a pH of 4 to 11, more preferably 5 to 10, even more preferably 5 to 9 when dissolved in demineralised water at 4g/L, 293K.

13. Use according to any one of the preceding claims, wherein the composition is a cleaning composition comprising:

a) 1 to 30 wt% primary alkyl sulfate surfactant;

c) 1 to 10 wt% of a rhamnolipid biosurfactant;

wherein the primary alkyl sulfate is C ₁₀ -C ₂₀ Alkyl sulfate.