阅读说明：本技术 鼠李糖脂在表面活性剂体系中的用途 (Use of rhamnolipids in surfactant systems ) 是由 P·S·史蒂文森 N·J·帕里 P·K·贾伊斯沃 V·瓦凯利 于 2019-07-11 设计创作，主要内容包括：本发明涉及鼠李糖脂在用于手洗洗涤剂的表面活性剂体系中向消费者赋予在手上的温和性的感觉的用途。(The present invention relates to the use of rhamnolipids in surfactant systems for hand washing detergents to impart a feeling of mildness on the hands to the consumer.)

1. Use of rhamnolipids in a surfactant system for hand washing detergents to impart a feeling of mildness on the hands to the consumer.

2. Use according to claim 1, wherein the sensation of mildness on the hands persists after the hand washing process is ended, after the hands subsequently dry.

3. The use according to claim 1 or claim 2 wherein the rhamnolipid is present in the surfactant system at a level of 5-100 wt.%, preferably 10-90 wt.%, more preferably 15-80 wt.%, most preferably 15-50 wt.% of the surfactant system.

4. Use according to any preceding claim, wherein the hand wash detergent is a fluid detergent composition, preferably an aqueous detergent composition.

5. Use according to any preceding claim, wherein the hand wash detergent is a hand dishwashing composition, or a liquid laundry detergent composition for hand washing.

6. The use according to claim 5, wherein the rhamnolipid is present in the composition at a content of 1-20 wt. -%, preferably 1.25-15 wt. -%, more preferably 1.5-12.5 wt. -%, most preferably 2-10 wt. -%.

7. The use according to any one of the preceding claims, wherein the rhamnolipid comprises at least 50 wt.% of dirhamnolipid, more preferably at least 60 wt.% of dirhamnolipid, even more preferably 70 wt.% of dirhamnolipid, most preferably at least 80 wt.% of dirhamnolipid.

8. The use according to any one of the preceding claims wherein the rhamnolipid is of the formula Rha2C_8-12C_8-12The dirhamnolipid of (1).

Technical Field

The present invention relates to the use of rhamnolipids in a surfactant system for hand washing detergents.

Background

Hand washing detergents refer to detergents that involve consumers washing substrates with their hands. The fields of use mainly include laundry use (i.e. hand washing of laundry) and Hand Dishwashing (HDW) (i.e. hand washing of dishware and the like). Hand washing detergents involve intimate contact of the detergent liquid with the hands during the wash process, whether in the laundry or in the HDW. While formulation efficacy is an important attribute to restore consumer use, the sensory experience of the formulation and its use during and after use of the formulation by the consumer during washing leaves a lasting impression of whether the consumer has a good or bad experience with the product.

The sensory experience may include, for example, a pleasant color or scent on the product itself or during use. Another important sensory experience of consumers using hand washing detergents is the long-lasting feel left on the hands. This is important because the hand wash process involves the consumer's hands contacting the formulation and the resulting wash liquor, and the formulation can cause irritation to the skin.

There is a need for improved hand wash detergents that leave an improved feel on the hands. In particular, those which leave an improved sensation of mildness on the hands during the washing process, and a permanently improved sensation of mildness on the hands after the end of the hand washing process.

One way to address this is to include ingredients that enhance mildness, such as polyethylene glycol ingredients.

Disclosure of Invention

We have found that the use of rhamnolipids in surfactant systems for hand washing detergents imparts a feeling of mildness on the hands to the consumer. By using rhamnolipids, the necessity of using components such as polyethylene glycol is reduced or eliminated.

The present invention relates in a first aspect to the use of rhamnolipids in a surfactant system for hand washing detergents to impart a feeling of mildness on the hands to the consumer.

Preferably, the feeling of mildness on the hands persists after the hand washing process is completed, and the hands subsequently dry.

Preferably, in terms of use, the rhamnolipids are present in the surfactant system at a level of 5-100 wt%, preferably 10-90 wt%, more preferably 15-80 wt%, most preferably 15-50 wt% of the surfactant system.

Preferably, the hand wash detergent is a fluid detergent composition, preferably an aqueous detergent composition.

Preferably, the rhamnolipids are present in the composition in an amount of 1-20 wt.%, preferably 1.25-15 wt.%, more preferably 1.5-12.5 wt.%, most preferably 2-10 wt.%.

Preferably, the hand wash detergent is a manual dishwashing composition, or a liquid laundry detergent composition for hand washing.

Preferably, the rhamnolipid comprises at least 50 wt.% of dirhamnolipid, more preferably at least 60 wt.% of dirhamnolipid, even more preferably 70 wt.% of dirhamnolipid, most preferably at least 80 wt.% of dirhamnolipid.

Preferably, the rhamnolipid is of the formula Rha2C_8-12C_8-12The dirhamnolipid of (1).

Any preferred subject matter described herein can be combined with any other subject matter, particularly with two or more preferred subject matter.

Detailed Description

Hand washing

Hand washing detergents refer to detergents that involve consumers washing substrates with their hands. Preferred hand wash applications include primarily laundry applications (i.e. hand washing of laundry) and Hand Dishwashing (HDW) (i.e. hand washing of dishware and the like). Hand washing detergents involve the intimate contact of the detergent liquid with the hand during the washing process, whether during the laundering process or during the manual dishwashing process.

Rhamnolipid

Rhamnolipids 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 in E.Deziel et al Applied Microbiology and Biotechnology (2010)86: 1323-. Rhamnolipids are produced by Glycosurf, AGAE Technologies and Urumqi Unite Bio-Technology co. Rhamnolipids can be produced by strains of pseudomonas aeruginosa bacteria. Rhamnolipids can also be produced by recombinant cells of pseudomonas mendocina, wherein the recombinant cells comprise an increased activity of at least one of the enzymes a/P hydrolase, rhamnosyltransferase I or rhamnosyltransferase II, compared to the wild type of the cell.

Rhamnolipids fall into two main classes; mono and di rhamnolipids.

A mono rhamnolipid has a single rhamnose ring. A typical monorhamnolipid produced by Pseudomonas aeruginosa is L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (RhAC)₁₀C₁₀). It may be referred to as Rha-C₁₀-C₁₀Having the formula C₂₆H₄₈O₉. A mono rhamnolipid has a single rhamnose ring.

The IUPAC name is 3- [3- [ (2R,3R,4R,5R,6S) -3,4, 5-trihydroxy-6-methyloxirane-2-yl ] oxycarbonyloxy ] decanoic acid.

Dirhamnolipid has two rhamnose rings. A typical dirhamnolipid is L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (Rha 2C)₁₀C₁₀). Which may be referred to as Rha-Rha-C-₁₀-C-₁₀Having the formula C₃₂H₅₈O₁₃。

The IUPAC name is 3- [3- [4, 5-dihydroxy-6-methyl-3- (3,4, 5-trihydroxy-6-methyloxirane-2-yl) oxooxirane-2-yl ] oxodecanoyloxy ] decanoic acid.

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

In various publications, monorhamnolipids have the symbol Rha-, which may be abbreviated as Rh or RL 2. Similarly, dirhamnolipid has the symbol Rha-Rha or Rh-Rh-or RL 1. For historical reasons, "rhamnolipid 2" is a mono rhamnolipid and "rhamnolipid 1" is a di-rhamnolipid. This leads to some ambiguity in the usage of "RL 1" and "RL 2" in the literature.

In this patent specification we use the terms mono and di rhamnolipid to avoid this possible confusion. However, if abbreviations are used, R1 is a monorhamnolipid, R₂Is dirhamnolipid. For more information on confusion of terms in the prior art, see the description of US 4814272.

The following rhamnolipids have been detected, produced by the following bacteria: (C)_12:1，C_14:1Representing a fatty acyl chain with a double bond).

Rhamnolipids produced by pseudomonas aeruginosa (mono rhamnolipids):

Rha-C₈”C₁₀、Rha-C₁₀-C₈、Rha-C₁₀-C₁₀、Rha-C₁₀-C₁₂、Rha-C₁₀-C_12:1、Rha-C₁₂-C₁₀、Rha-C_12:1-C₁₀

rhamnolipids produced by pseudomonas aeruginosa (dirhamnolipid):

Rha-Rha-C₈-C₁₀、Rha-Rha-C₈-C_12:1、Rha-Rha-C₁₀-C₈、Rha-Rha-C₁₀-C₁₀、Rha-Rha-C₁₀-C_12:1、Rha-Rha-C₁₀-C₁₂、Rha-Rha-C₁₂-C₁₀、Rha-Rha-C_12:1-C₁₂、Rha-Rha-C₁₀-C_14:1

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

C₈-C₈、C₈-C₁₀、C₁₀-C₈、C₈”C_12:1、C_12:1-C₈、C₁₀-C₁₀、C₁₂-C₁₀、C_12:1-C₁₀、C₁₂-C₁₂、C_12:1-C₁₂、C₁₄-C₁₀、C_14:1-C₁₀、C₁₄-C₁₄。

rhamnolipids produced by pseudomonas aeruginosa (only mono rhamnolipids):

Rha-C₁₀-C₈、Rha-C₁₀-C₁₀、Rha-C₁₂-C₁₀、Rha-C_12:1-C₁₀、Rha-C₁₂-C₁₂、Rha-C_12:1-C₁₂、Rha-C₁₄-C₁₀、Rha-C_14:1-C₁₀

rhamnolipids produced by burkholderia mallei (dirhamnolipid only):

Rha-Rha-C₁₄-C₁₄。

rhamnolipids produced by burkholdera (pseudomonas) plantarii (only dirhamnolipid):

Rha-Rha-C₁₄-C₁₄。

the American Type Culture Collection (ATCC) has over 100 strains of Pseudomonas aeruginosa in records. Still other strains are available only from manufacturers of commercial rhamnolipids. In addition, potentially thousands of strains have been isolated by various research institutions around the world. Some work has gone into grouping them. Each strain has different characteristics including how much rhamnolipid is produced, what type of rhamnolipid is produced, what is metabolized by it, and conditions under which it is grown. Only a low percentage of strains have been extensively studied.

By evaluation and screening, strains of Pseudomonas aeruginosa can be isolated to produce rhamnolipids at higher concentrations and more efficiently. Strains that produce fewer by-products and metabolize different raw materials or contaminants may also be selected. This production is greatly influenced by the environment in which the bacteria are growing.

A typical dirhamnolipid is L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (formula C)₃₂H₅₈O₁₃Rha2C₁₀C₁₀)。

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

Preferably, the rhamnolipids are present in the composition in an amount of 1-20 wt.%, preferably 1.25-15 wt.%, more preferably 1.5-12.5 wt.%, most preferably 2-10 wt.%.

The rhamnolipids are preferably selected from:

rhamnolipids produced by pseudomonas aeruginosa (mono rhamnolipids):

Rha-C₈-C₁₀、Rha-C₁₀-C₈、Rha-C₁₀-C₁₀、Rha-C₁₀-C₁₂、Rha-C₁₀-C_12:1、Rha-C₁₂-C₁₀、Rha-C_12:1-C₁₀

rhamnolipids produced by pseudomonas aeruginosa (only mono rhamnolipids):

Rha-C₁₀-C₈、Rha-C₁₀-C₁₀、Rha-C₁₂-C₁₀、Rha-C_12:1-C₁₀、Rha-C₁₂-C₁₂、Rha-C_12:1-C₁₂、Rha-C₁₄-C₁₀、Rha-C_14:1-C₁₀

monorhamnolipids that can also be produced from P.lodoides [ Cha et al, Bioresource technol.2008.99(7):2192-9] by introducing the rhlA and rhlB genes of P.aeruginosa

-rhamnolipids produced by pseudomonas aeruginosa (dirhamnolipid):

Rha-Rha-C₈-C₁₀、Rha-Rha-C₈-C_12:1、Rha-Rha-C₁₀-C₈、Rha-Rha-C₁₀-C₁₀、Rha-Rha-C₁₀-C_12:1、Rha-Rha-C₁₀-C₁₂、Rha-Rha-C₁₂-C₁₀、Rha-Rha-C_12:1-C₁₂、Rha-Rha-C₁₀-C_14:1

rhamnolipids produced by burkholderia mallei (dirhamnolipid only):

Rha-Rha-C₁₄-C₁₄。

rhamnolipids produced by burkholdera (pseudomonas) plantarii (dirhamnolipid only):

Rha-Rha-C₁₄-C₁₄。

-rhamnolipids produced by pseudomonas aeruginosa, not originally identified as mono-or di-rhamnolipids:

C₈-C₈、C₈-C₁₀、C₁₀-C₈、C₈-C_12:1、C_12:1-C₈、C₁₀-C₁₀、C₁₂-C₁₀、C_12:1-C₁₀、C₁₂-C₁₂、C_12:1-C₁₂、C₁₄-C₁₀、C_14:1-C₁₀、C₁₄-C₁₄。

the rhamnolipid is preferably L-rhamnosyl-beta-hydroxydecanoyl-beta-hydroxydecanoate (formula C)₂₆H₄₈O₉RhaC (C)₁₀C₁₀)。

Preferably, the rhamnolipid comprises at least 50 wt.% of dirhamnolipid, more preferably at least 60 wt.% of dirhamnolipid, even more preferably 70 wt.% of dirhamnolipid, most preferably at least 80 wt.% of dirhamnolipid.

Preferably, the rhamnolipid is of the formula Rha2C_8-12C_8-12The dirhamnolipid of (1). Preferred alkyl chain lengths are C₈-C₁₂. The alkyl chain may be saturated or unsaturated.

The most preferred dirhamnolipid is of the formula Rha2C_8-12C_8-12An example of a dirhamnolipid of (a), herein referred to as rhamnolipid R2, may be supplied from Evonik.

Hand washing detergent composition

Hand wash detergent compositions are cleaning compositions that can be used to clean one or more substrates.

The composition is preferably a fluid detergent composition, more preferably an aqueous detergent composition.

Preferably, the hand wash detergent is a manual dishwashing composition, or a liquid laundry detergent composition for hand washing.

Preferably, the pH of the manual dishwashing composition is from 4 to 8, more preferably from 4.5 to 7.5, when the liquid laundry detergent is dissolved in demineralized water at 293K at 4 g/L.

Preferably, the pH of the liquid laundry detergent composition is from 6 to 11, more preferably from 7 to 9, when the liquid laundry detergent is dissolved in demineralized water at 293K at 4 g/L.

A second anionic surfactant

In a hand wash composition according to the second aspect of the invention, the composition comprises a second different anionic surfactant.

The composition comprises from 1 to 20 wt%, preferably from 1.5 to 17.5 wt%, more preferably from 2 to 15 wt%, most preferably from 5 to 15 wt% of a second different anionic surfactant.

In the handwash composition of the second aspect of the invention, preferably the rhamnolipids are present in the surfactant system at a level of 10-90 wt%, more preferably 15-80 wt%, most preferably 15-50 wt% of the surfactant system.

Preferably, in the use aspect of the first aspect of the invention, the composition comprises a second, different anionic surfactant.

When a second different anionic surfactant is used, preferably the rhamnolipid is present in the surfactant system at a level of 10-90 wt%, more preferably 15-80 wt%, most preferably 15-50 wt% of the surfactant system.

In all aspects of the invention, preferably the second anionic surfactant is selected from C₁₀To C₂₀Straight chain alkyl benzene sulfonate, C₁₀To C₂₀Alkyl sulfates, C₁₀To C₂₀Alkyl ether sulfates and mixtures thereof. More preferably, the second different anionic surfactant is a mixture of the aforementioned anionic surfactants. More preferably, the second different anionic surfactant (b) is C₁₀To C₂₀Linear alkyl benzene sulfonate and C₁₀To C₂₀Mixtures of alkyl ether sulfates. Most preferably, C₁₀To C₂₀Linear alkyl benzene sulfonate and C₁₀To C₂₀The mixture of alkyl ether sulfates is a mixture in a ratio of 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70: 30.

Additional surfactants

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 additional surfactant.

These are preferably selected from additional anionic, nonionic and zwitterionic surfactants.

Generally, the nonionic and anionic surfactants of the surfactant system may be selected from "Surface Active Agents", Vol.1, Schwartz & Perry, Interscience 1949; volume 2, Schwartz, Perry & Berch, Interscience 1958; surfactants as described in the current version of "McCutcheon's Emulsifiers and Detergents", published by Manufacturing conditioners Company, or "Tenside Taschenbuch", H.Stache, 2 nd edition, Carl Hauser Verlag, 1981. Preferably, the surfactant used is saturated.

Preferred nonionic detergent compounds which may be used include the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides, with alkylene oxides, especially ethylene oxide, alone or together 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 to 40EO, preferably 7 to 9 EO.

Preferred anionic detergent compounds which may be used are typically water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.

Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, in particular those obtained by sulphating alcohols prepared, for example, from tallow or coconut oil, alkyl C₁₀To C₂₀Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C₁₀To C₁₅Sodium benzenesulfonate; and sodium alkyl glyceryl ether sulfates, particularly those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. Preferred anionic detergent compounds are C₁₁-C₁₅Sodium alkyl benzene sulfonate and C₁₂-C₁₄Sodium alkyl sulfate. Also suitable are surfactants such as those described in EP-A-328177 (Unilever), alkyl polyglycoside surfactants described in EP-A-070074, and alkyl monoglycosides which exhibit resistance to salting out.

Preferred surfactant systems are mixtures of anionic and nonionic detergent active materials, especially the groups and examples of anionic and nonionic surfactants indicated in EP-A-346995 (Unilever). Particularly preferred are surfactant systems of the aforementioned anionic surfactants with C₁₂-C₁₆Primary alcohol 3-7EO ethoxylates.

Preferred zwitterionic surfactants include cocamidopropyl betaine. The preferred content of zwitterionic surfactant is 0.1-5 wt.%, preferably 0.5-4 wt.%.

Additional ingredients

The hand wash composition may comprise any of these further preferred ingredients, depending on whether the hand wash composition is a manual dishwashing composition or a liquid laundry detergent composition for hand washing.

Builders or complexing agents

Builder materials may be particularly useful in liquid laundry detergent compositions for hand washing.

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

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate, and organic sequestrants, 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 best known representatives, such as zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and the P-type zeolites described in EP- ｃA-0,384,070.

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

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

The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15% by weight. Aluminosilicates are materials having the general formula:

0.8-1.5M₂O·Al₂O₃·0.8-6SiO₂

wherein M 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. In the above formula, the preferred sodium aluminosilicate contains 1.5 to 3.5 SiO₂And (4) units. They can be easily prepared by reaction between sodium silicate and sodium aluminate, as described in detail 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 may be used. In the art, the term "phosphate" includes diphosphate, triphosphate, and phosphonate species. Other forms of builders include silicates, such as soluble silicates, metasilicates, layered silicates (e.g., SKS-6 from Hoechst).

When a laundry composition is used, preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e. comprising less than 1 wt% phosphate. Preferably, if a builder is included, the laundry detergent formulation is carbonate built.

Fluorescent agent

These materials may be particularly useful in liquid laundry detergent compositions for hand washing.

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

The total amount of fluorescer or fluorescers used in the composition is typically 0.005 to 2 wt%, more preferably 0.01 to 0.1 wt%. Preferred classes of fluorescers are: distyrylbiphenyl compounds such as Tinopal (trademark) CBS-X; diamine stilbene disulfonic acid compounds such as Tinopal DMS pure Xtra and Blankophor (trade Mark) HRH; and pyrazoline compounds such as Blankophor SN. Preferred fluorescent agents are: sodium 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d ] triazole, 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-morpholinyl-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.

It is preferred that the aqueous solution used in the method has a fluorescent agent. When the fluorescent agent is present in the aqueous solution used in the method, it is preferably in the range of 0.0001g/L to 0.1g/L, preferably 0.001g/L to 0.02 g/L.

Dye material

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 as color indices (Society of Dyers and Colourists and the American Association of Textile Chemists and Colourists).

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

Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anion, which may or may not be charged. Azine dyes preferably carry a net anionic or cationic charge.

Preferred non-hueing dyes are selected from blue dyes, most preferably anthraquinone dyes with sulfonate groups and triphenylmethane dyes with 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 93:1, 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 dye provide an attractive color to the wash liquor.

Blue or violet shading dyes are most preferred. Hueing dyes deposit onto fabrics during the washing or rinsing step of the washing process, providing the fabrics with a visible hue (hue). In this regard, the dye imparts a blue or violet color to white laundry with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white garment used in this test was a bleached non-mercerized (non-mercerized) knitted cotton sheet.

Hueing dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO2006/032397(Unilever), WO2006/045275(Unilever), WO2006/027086(Unilever), WO2008/017570(Unilever), WO2008/141880(Unilever), WO2009/132870(Unilever), WO2009/141173(Unilever), WO2010/099997(Unilever), WO2010/102861(Unilever), WO2010/148624(Unilever), WO2008/087497(P & G), WO2011/011799(P & G), WO2012/054820(P & G), WO2013/142495(P & G) and WO2013/151970(P & G).

Mixtures of hueing dyes may be used.

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

The monoazo dyes preferably contain heterocycles, 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 WO2013/142495 and WO 2008/087497.

Most preferred shading dyes are selected from direct violet 9, direct violet 99, direct violet 35, solvent violet 13, disperse violet 28, dyes having the structure

Perfume

Preferably, the composition comprises a perfume. The perfume is preferably present in the range of 0.001 to 3 wt%, most preferably 0.1 to 1 wt%. Examples of many suitable perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide, published by CFTA Publications, and the OPD 1993Chemicals layers Directory, 80 years edition, published by Schnell Publishing Co.

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

In the perfume mixture, preferably 15 to 25% by weight is 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 citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

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

Polymer and method of making same

The composition may comprise 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.

Thickening polymers such as anionic acrylic polymers may be included, examples include Acusol 820.

Enzyme

These materials may be particularly useful in liquid laundry detergent compositions for hand washing.

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

Preferably, the laundry compositions of the present invention comprise from 0.0001 wt% to 0.1 wt% protein of each enzyme.

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: humicola (Humicola) (synonym thermophilic fungi (Thermomyces)), for example from h.lanuginosa (t.lanuginosus) as described in EP 258068 and EP 305216 or from h.insolens as described in WO 96/13580; pseudomonas lipases, for example from pseudomonas alcaligenes (p. alcaligenes) or pseudomonas pseudoalcaligenes (p. pseudoalcaligenes) (EP 218272), pseudomonas cepacia (p.cepacia) (EP 331376), pseudomonas stutzeri (GB 1,372,034), pseudomonas fluorescens (p. fluoroscens), pseudomonas strains SD 705(WO 95/06720 and WO 96/27002), p.wisconsinensis (WO 96/12012); bacillus lipases, for example 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).

Further examples are lipase variants, such as those described in WO 92/05249, WO 94/01541, EP 407225, EP 260105, 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^TMAnd Lipolase Ultra^TM、Lipex^TMAnd Lipoclean^TM(Novozymes A/S)。

The process of the invention may be carried out in the presence of a phospholipase classified under EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that is active on phospholipids.

Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified at the outer (sn-1) and middle (sn-2) positions with two fatty acids and phosphorylated at the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes involved in phospholipid hydrolysis. Can distinguish between various types of phospholipase activity, including phospholipase A₁And A₂Which hydrolyses one fatty acyl group (at the sn-1 and sn-2 positions, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze the remaining fatty acyl groups in lysophospholipid.

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

The enzyme and the photo-bleach may exhibit some interaction, and should be selected such that this interaction is not negative. By encapsulating one or the other enzyme or photo-bleach and/or other barrier within the product, certain negative interactions can be avoided.

Suitable proteases include those of animal, vegetable or microbial origin. Microbial sources are preferred. 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^TM、Savinase^TM、Primase^TM、Duralase^TM、Dyrazym^TM、Esperase^TM、Everlase^TM、Polarzyme^TMAnd Kannase^TM(Novozymes A/S)、Maxatase^TM、Maxacal^TM、Maxapem^TM、Properase^TM、Purafect^TM、Purafect OxP^TM、FN2^TMAnd FN3^TM(Genencor International Inc.)。

The process of the invention may be carried out in the presence of a cutinase classified under EC 3.1.1.74. The cutinase to be 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 (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, such as particular strains of Bacillus licheniformis described in more detail in GB 1,296,839, or strains of Bacillus disclosed in WO 95/026397 or WO 00/060060. A commercially available amylase is Duramyl^TM、Termamyl^TM、Termamyl Ultra^TM、Natalase^TM、Stainzyme^TM、Fungamyl^TMAnd BAN^TM(Novozymes A/S)、Rapidase^TMAnd 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: fungal cellulases produced by bacillus, pseudomonas, humicola, fusarium, thielavia, acremonium, e.g. from humicola insolens, thielavia terrestris, myceliophthora thermophila and fusarium oxysporum disclosed in US4,435,307, US5,648,263, US5,691,178, US5,776,757, WO 89/09259, WO 96/029397 and WO 98/012307. Commercially available cellulases include Celluzyme^TM、Carezyme^TM、Celluclean^TM、Endolase^TM、Renozyme^TM(Novozymes A/S)、Clazinase^TMAnd Puradax HA^TM(Genencor International Inc.) and KAC-500(B)^TM(Kao Corporation)。

Suitable peroxidasesOxidase enzymes include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g., Coprinus cinereus, and variants thereof, such as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include Guardzyme^TMAnd Novozym^TM51004(Novozymes A/S)。

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

Enzyme stabilizer

Any enzyme present in the composition may be stabilized using conventional stabilizers, for example polyols such as propylene glycol or glycerol; a sugar or sugar alcohol; lactic acid; boric acid or a boric acid derivative, for example an aromatic borate ester, or a phenyl boronic acid derivative, for example 4-formylphenyl boronic acid, and the compositions may be formulated as described, for example, in WO 92/19709 and WO 92/19708.

When the alkyl group is long enough to form a branched or cyclic chain, the alkyl group includes branched, cyclic, and linear alkyl chains. The alkyl group is preferably linear or branched, most preferably linear.

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

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

Examples

The purpose of the panel evaluation was to determine and measure the differences in specific organoleptic properties of the product compared to the control formulation. This was done by blind testing of the product. The study conducted ensured that all panelists seen and evaluated all prototype and control products in a random order. Panelists were trained panelists: these were panelists who were screened for sensory acuity and trained analytical techniques, 12-15 of which were included.

The panelists worked on the 0-10 scale with two anchor points, 1 being not very mild and 9 being very mild.

After the wash process, the panelists waited for 10 minutes while their hands were dripping dry. They then evaluated the gentleness of their hands.

For the mildness attribute, the following sensory attributes were measured:

the gentle feel on the hand after drying the hand refers to the creamy/laminar impression felt on the hand after drying the hand; the assessment was made by sliding between the hand surfaces with the fingers and feeling on the other fingers with the thumb, and again the measurements were made on a scale between no gentleness at all and very gentleness.

Formulation used-control

The control formulations all had acceptable viscosities of 1180 to 1610 centipoise (cP).

Viscosity was measured using an Anton Paar ASC rheometer at 25 deg.C-set using Bob and reported at 23s^-1Viscosity measured at shear rate

Formulations for use-according to the invention

Rhamnolipid R2 is a dirhamnolipid supplied by Evonik.

The formulations according to the invention all have acceptable viscosities between 1350 and 1520 centipoise (cP).

Viscosity was measured using an Anton Paar ASC rheometer at 25 deg.C-set using Bob and reported at 23s^-1Viscosity measured at shear rate.

Results table of long lasting mildness attributes

Long lasting mildness of 1 compared to controls 1 to 3

Formulation 1 gave a statistically significant improvement in this attribute compared to controls 1 to 3 (Tukey's HSD test, 95% confidence interval).

2 Long-term durable mildness compared to controls 1 to 3

Formulation 2 gave a statistically significant improvement in this attribute compared to controls 1 to 3 (Tukey's HSD test, 95% confidence interval).

3 Long-term durable mildness compared to controls 1 to 3

Formulation 3 gave a statistically significant improvement in this attribute compared to controls 1 to 3 (Tukey's HSD test, 95% confidence interval).

4 Long-term durable mildness compared to controls 1 to 3

Formulation 4 gave a statistically significant improvement in this attribute compared to controls 1 to 3 (Tukey's HSD test, 95% confidence interval).

5 Long-term durable Mild Properties compared to controls 1 to 3

Formulation 5 gave a statistically significant improvement in this attribute compared to controls 1 to 3 (Tukey's HSD test, 95% confidence interval).

As can be seen from this data, the use of rhamnolipids in surfactant systems for hand washing detergents imparts a feeling of mildness on the hands to the consumer. This sensation is seen especially after the hand washing process is over, after the hands are subsequently dried, with the mild sensation on the hands remaining.