EP4036199A1

EP4036199A1 - Detergent composition

Info

Publication number: EP4036199A1
Application number: EP21154557.9A
Authority: EP
Inventors: designation of the inventor has not yet been filed The
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2021-02-01
Filing date: 2021-02-01
Publication date: 2022-08-03

Abstract

The present invention relates to a solid laundry detergent composition, more specifically to laundry detergent composition comprising low levels of alkaline builders.It is an object of the present invention to provide a solid laundry detergent composition having low carbonate levels and low silicate levels which gives good solubility profile, good cleaning profile, good stability profile, good fabric care profile and good freshness profile.The present inventors have surprising found that the fabric care benefits and stain removal performance of solid laundry detergent composition having low carbonate levels and low silicate levels can be achieved by combination of an anionic surfactant with amphoteric surfactant and a silicone surfactant.

Description

Field of the invention

The present invention relates to a solid laundry detergent composition, more specifically to solid laundry detergent composition comprising low levels of alkaline builders.

Background of the invention

Consumers of solid laundry detergent compositions desire that the laundry composition provides good fabric cleaning performance against a wide variety of soil types and also has very good dispensing and dissolution profiles. Especially consumers who hand-wash fabrics also desire for a laundry composition which is less harsh on hands and on fabrics.
Laundry detergent composition for cleaning fabrics have been known for many years to include anionic detersive surfactant, particularly linear alkyl benzene sulphonate anionic surfactant. Formulators of the detergent composition incorporate anionic detergents into solid laundry detergent composition in order to provide a good fabric-cleaning benefit. Laundry composition are generally added to water to form a solution, the water usually includes free cations, such as calcium and magnesium cations, these interact negatively with the anionic detersive surfactant and lead to a reduction in the anionic detersive surfactant activity. In order to mitigate the tendency of anionic detersive surfactant to react with free cations in the wash liquor and precipitate out of solution, builders such as zeolite, silicates and carbonate, are incorporated into the composition. These builders sequester free calcium and magnesium cations. In addition to its role as builder the carbonate and silicate builders also increase the pH of the wash liquor which is beneficial at removing stains.
However, when carbonate and silicate builders are incorporated in laundry detergent compositions they interact with the free calcium and magnesium cations and form complexes, these complexes are water-insoluble and in extreme hard water conditions the water-insoluble complex may deposit onto the fabric resulting in poor whiteness maintenance and may cause poor fabric integrity. In addition, the increased alkalinity of detergent compositions that comprise high levels of carbonate builders and silicate builders is harsh on fabrics and hands of the user. Furthermore, the high pH levels can negatively impact some cleaning actives. Additionally, it is also desired to cut the levels of carbonates in order to deliver low chemical formulations.
Thus, there remains a need for a solid laundry detergent composition comprising an anionic detersive surfactant having a good fabric-cleaning performance, especially a good particulate, oily and greasy stain cleaning performance, good whiteness maintenance, and very good dispensing and dissolution profiles while the composition has low levels of alkaline builders.
Prior art documents which provide detergent compositions with lower levels of carbonate and silicate alkaline builders are known.
US2018094228A1 (Procter & Gamble) discloses a solid free flowing particulate laundry detergent composition having a low pH profile and providing good cleaning profile and good fabric care profile. The composition includes anionic surfactant, 0 to 8 wt.% levels of sodium carbonate, 0 to 8 wt.% sodium silicate.
However, there is still a need in the art for a solid laundry detergent composition that comprise an anionic surfactant, low carbonate levels and preferably low silicate levels, while maintaining excellent cleaning performance. It is also desired to provide a solid laundry detergent composition with a pH from 7 to 10.5 which provides benefits such as low or no deposition of residues on fabrics and associated improvement in whiteness, improved bleachable stain removal benefits.
It is thus an object of the present invention to provide a solid laundry detergent composition having a low levels of carbonate salt and silicate salt.
It is another object of the present invention to provide a solid laundry detergent composition having low carbonate levels and low silicate levels which gives good solubility profile, good cleaning profile, good stability profile, good fabric care profile and good freshness profile.

Summary of the invention

The present inventors have surprising found that the fabric care benefits and stain removal performance of solid laundry detergent composition having low carbonate levels and low silicate levels can be achieved in the composition by combination of an anionic surfactant with amphoteric surfactant and a silicone surfactant.
According to a first aspect of the present invention disclosed is a solid detergent composition comprising:

i) anionic surfactant;
ii) an amphoteric surfactant;
iii) a silicone surfactant;
iv) 0 wt.% to 20 wt.% carbonate salt; and,
v) 0 wt.% to 10 wt.% silicate salt.

According to a second aspect of the present invention disclosed is a method of laundering a textile surface with the detergent composition according to any one of the preceding claims comprising the steps of:

i) preparing a wash liquor by mixing the detergent composition according to the first aspect with a liquid, preferably water;
ii) soaking said textile surface in the wash liquor for a predetermined period of time; and,
iii) optionally rinsing the textile surface.

According to a third aspect of the present invention disclosed is use of an anionic surfactant, amphoteric surfactant and a silicone surfactant or derivatives thereof in a detergent composition comprising from 0 wt.% to 20 wt.% carbonate salt and 0 wt.% to 10 wt.% silicate salt to provide improved stain removal performance.
A solid detergent composition according to the present disclosure encompasses a variety of spray-dried or granulated forms including, for example powder, particulates; cast and extruded forms including, for example, solids, pellets, blocks, bars, and tablets. It should be understood that the term "solid" refers to the state of the detergent composition under the expected conditions of storage and use of the solid detergent composition. In general, it is expected that the detergent composition will remain a solid when provided at a temperature of up to about 37° C and preferably greater than 50°C.
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.

Detailed description of the invention

According to the first aspect of the present invention, disclosed is a solid detergent composition having 0 wt.% to 20 wt.% carbonate salt; 0 wt.% to 10 wt.% silicate salt and which includes an anionic surfactant, an amphoteric surfactant, a silicone surfactant.

Anionic surfactant

According to a first aspect of the present invention disclosed solid laundry composition includes an anionic surfactant. Examples of anionic surfactant are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
Suitable anionic surfactants include those selected from the group consisting of alkyl sulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates, alkyl carboxylates, alkyl amido ether carboxylates, alkyl succinates, fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates, fatty alkyl sulfoacetates, alkyl phosphates, and mixtures of two or more thereof.
Suitable anionic surfactant includes, for example, the alkyl benzene sulphonic acids and their salts, alkoxylated or non-alkoxylated alkyl sulfate. The anionic surfactant may be present in the form of acid or in neutralized salt form. The anionic surfactant may be liner, branched or combinations thereof.
Nonlimiting examples of anionic surfactants useful herein include: C₁₀ to C₂₀ primary, branched chain and random alkyl sulfates (AS); C₁₀ to C₁₈ secondary (2,3) alkyl sulfates; C₁₀ to C₁₈ alkyl alkoxy sulfates (AES) wherein x is from 1-30; C₁₀ to C₁₈ alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443 ; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008 , 181 and US 6,020,303 ; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243 , WO 99/05242 and WO 99/05244 ; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS). Such surfactants include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials.
Exemplary anionic surfactants are the alkali metal salts of C₁₀ to C₁₈ alkyl benzene sulfonic acids, preferably C₁₁ to C₁₄ alkyl benzene sulfonic acids. In one aspect, the alkyl group is linear. Such linear alkyl benzene sulfonates are known as "LAS". Such surfactants and their preparation are described for example in U.S. Patent Nos. 2,220,099 and 2,477,383 . Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁ to C₁₄ LAS, e.g., C₁₂ LAS, are a specific example of such surfactants.
Another exemplary type of anionic surfactant comprises linear or branched ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O-(C₂H₄O)_n-SO₃M wherein R' is a C₈ to C₂₄ alkyl (linear, branched, saturated or unsaturated) group , n is from about 1 to 20, preferably 1 to 12, and M is a salt-forming cation. In a specific embodiment, R' is C₁₀ to C₁₈ alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a C₁₂ to C₁₆ from about 1 to 6 and M is sodium. The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Examples include sodium laureth sulphate, ammonium laureth sulphate, sodium trideceth sulphate.
Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention. Specific examples of non-alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C₈ to C₂₀ fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula: R"OSO₃ ^-M⁺ wherein R" is typically a C₈ to C₂₀ alkyl (linear or branched, saturated or unsaturated) group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R" is a C₁₀ to C₁₅ alkyl group, and M is alkali metal, more specifically R" is C₁₂ to C₁₄ alkyl and M is sodium. Examples include sodium lauryl sulphate, ammonium lauryl sulphate and sodium coco sulphate.
Specific, non-limiting examples of anionic surfactants useful herein include a) C₁₁ to C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀ to C₂₀ primary, branched-chain and random alkyl sulfates (AS); c) C₁₀ to C₁₈ secondary (2,3)-alkyl sulfates having following formulae:
wherein M is hydrogen or a cation which provides charge neutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can either be a hydrogen atom or a cation depending upon the form isolated by the artisan or the relative pH of the system wherein the compound is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9; d) C₁₀ to C₁₈ alkyl alkoxy sulfates (AES) wherein preferably z is from 1 to 30; e) C₁₀ to C₁₈ alkyl alkoxy carboxylates preferably comprising 1 to 5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in U.S. Patent Nos. 6,020,303 and 6,060,443 ; g) mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Patent Nos. 6,008,181 and 6,020,303 ; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243 , WO 99/05242 , WO 99/05244 , WO 99/05082 , WO 99/05084 , WO 99/05241 , WO 99/07656 , WO 00/23549 , and WO 00/23548 . ; i) methyl ester sulfonate (MES); and j) alphaolefin sulfonate (AOS).
Anionic surfactants may exist in an acid form and the acid form may be neutralized to form a surfactant salt. Typical agents for neutralization include a metal counter ion base such as a hydroxide, e.g., NaOH or KOH. Further agents for neutralizing anionic surfactants include ammonia, amines, or alkanolamines. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art, for example, 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may be done to a full or partial extent, e.g. part of the anionic surfactant mix may be neutralized with sodium or potassium and part of the anionic surfactant mix may be neutralized with amines or alkanolamines.
Preferably the anionic surfactant is a non-soap anionic surfactant. The term "soap" is used herein in its popular sense, i.e., the alkali metal or alkanol ammonium salts of aliphatic, alkanes, or alkene monocarboxylic acids. Sodium, potassium, magnesium, mono-, di- and tri-ethanol ammonium cations, or combinations thereof, are the most suitable for purposes of this invention.
Preferably the anionic surfactant is selected from alkyl sulphate surfactant, alkyl sulphonate surfactant, alkyl ether sulphonate surfactant or combinations thereof. Non-limiting examples of the preferred anionic surfactant includes linear alkyl benzene sulphonate, lauryl ether sulfate, primary alkyl sulfate, methyl ester sulphonate or combinations thereof.
Preferably the anionic surfactant includes 0 wt.% to 10 wt.% alkyl sulfates, preferably 0 wt.% to 5 wt.% alkyl sulfates, preferably PAS. The anionic surfactant may also include from 0 wt.% to 10 wt.% MES, preferably 0 wt.% to 5 wt.% MES. The anionic surfactant may be an SLES, preferably included in the composition in an amount from 0 wt.% to 10 wt.%, preferably 0 wt.% to 5 wt.%.
The detergent composition of the present invention includes from 2 wt.% to 50 wt.% of an anionic surfactant, still preferably 2 wt.% to 40 wt.% anionic surfactant. Preferably the detergent composition comprises at least 4 wt.%, still preferably at least 5 wt.%, still preferably at least 10 wt.%, most preferably at least 15 wt.% of the anionic surfactant, but typically not more than 45 wt.%, still preferably not more than 40 wt.%, still further preferably not more than 35 wt.%, still more preferably not more than 30 wt.% and most preferably not more than 20 wt.% of an anionic surfactant based on the weight of the detergent composition.

Silicone surfactant

The detergent composition according to the present invention includes a silicone surfactant. The silicone surfactant comprises a hydrophobic silicone group and a pendant hydrophilic group. The silicone surfactant has a polysiloxane group which is modified. Preferably the polysiloxane hydrophobic group is modified with one or more pendant hydrophilic polyalkylene oxide groups. It may also preferably be a polybetaine-modified polysiloxane surfactant having a polysiloxane hydrophobic group modified with polybetaine group which is preferably grafted through hydrosilation reaction.
Preferred silicone surfactant which can be used according to the present invention includes polydialkyl siloxane, preferably polydimethyl siloxane to which a hydrophilic group(s), such as polyethylene oxide, has been grafted through a hydrosilation reaction. The process results in an alkyl pendant (AP type) copolymer, in which the hydrophilic groups are attached along the siloxane backbone through a series of hydrolytically stable Si-C bond.
Preferably the silicone surfactant is a polydialkyl siloxane surfactant which has the general formula (I) or (II) as given herein below:

wherein PE represents a nonionic group.
Preferably PE is represented as

-CH₂-(CH₂)_p-O-(EO)_m(PO)_n-Z, .. (a)

where EO representing ethylene oxide, PO representing propylene oxide, "x" is a number that ranges from about 0 to about 100, "y" is a number that ranges from about 1 to 100, "m", "n" and "p" are numbers that range from 0 to 50, m+n ≥ 1 and Z represents hydrogen or R wherein each R independently represents a lower (C₁ to C₆) straight or branched alkyl. Preferably, "p" is a number from 0 to 6, and R is methyl.
In the above formula (I) and (II) PE may also be represented as
preferably PE is represented as
Preferred silicone surfactant having the general formula (III) may be represent with the formula:
PA= -(C₂H₄O) _a (C₃H₆O) _b R

or
wherein "x" represent a number that ranges from 0 to 100, preferably x is 0 or 1 and "y" represent a number that ranges from 1 to 100, preferably y is at least 1. "a" and "b" represent numbers that independently range from 0 to 60, a+b≥1, and each R is independently H or a lower straight or branched (C₁ to C₆) alkyl. Preferably the R is hydrogen, methyl or butyl and the weight ratio of EO:PO is from 100:0 to 40:60. Preferably the weight ratio in percentage of EO (C₂H₄O, ethyleneoxy) to PO C₃H₆O, propyleneoxy) may vary from 100:0 to 0:100. A preferred silicone surfactant having the above formula includes x + y of 24 to 30, y of 4 to 7, the ratio of a/b being 0.25, R being H, PA having a molecular weight of between 800 and 950, and the silicone surfactant having a molecular weight of between 5,500 and 6,500. A preferred silicone surfactant satisfying these criteria is available under the name ABIL^® B 8852. A preferred silicone betaine surfactant is provided where x + y is 6 to 21, y is 4 to 7, and the molecular weight of the silicone betaine surfactant is between 2,000 and 3,000. A silicone surfactant generally satisfying this criteria is available under the name ABIL^® B 9950.
Another class of preferred silicone surfactant is an end-blocked (AEB type). Preferred AEB type silicone surfactants have the following general formula (IV):

R=-(CH₂)₃,-O-(C₂H₄O)_x(C₃H₆O)_y-H

wherein x represents 0 to 100, y represents 1 to 100, x + y represent 1 to 200. A preferred AEB type silicone surfactant is available under the name ABIL^® EM 97.
Preferably the silicone surfactant is a trisiloxane based surfactant having the formula
wherein R₁ and R₂ are each independently an alkyl having 1 to 3 carbon atoms or C_nH_2nO[C₂H₄O]_y [C₃H₆O], Q provided R₁ and R₂ are not the same, "a" is 0 to 2, "n" has a value from 2 to 4; "y" has a value of 3 to 10; "z" has a value from 0 to 5; Q is selected from the group consisting of hydrogen and a branched or straight chain alkyl having 1 to 4 carbon atoms. Preferably "a" is 0 to 1, "n" is 2 to 4, "y" is 5 to 9, "z" is 0 to 3 and "Q" is a 1 to 3 straight alkyl.
Preferred silicone surfactant includes but is not limited to 1,1,1,3,5,5,5-heptamethyl trisiloxane, polyalkylene oxide modified, 1,1,3,3,5,5,5-heptamethyl trisiloxane, polyalklyene oxide modified, or 1,1,3,3,3 pentamethyl disiloxane, polyalkylene oxide modified.
Another preferred silicone surfactant of the trisiloxane type has the formula:
wherein n=2 to 4, y=3 to 10, z= 0 to 5, and where R is either an alkyl having 1-4 carbon atoms or R is an OH or H group, provided that when z = 0, R = H and when z = 1 to 5 R = OH or )-alkyl having 1 to 4 carbon atoms.
Preferably the trisiloxane type silicone surfactant of general formula (VI) has a structure
wherein y=6 to 10, and most preferably wherein y=8.
Silicone surfactants herein described are commercially available under the tradename SILWET^® and includes Silwet L-77 (from Supreme Silcione) or polyether or polybetaine polysiloxane copolymer under the tradename ABIL^®. Preferred silicone surfactants are sold under the SILWET trademark or under the ABIL^® B trademark.
The silicone surfactant can be provided in the detergent composition of the invention in an amount from 0.05 wt. % to 20 wt. %, preferably 0.1 wt.5 to 10 wt.5 of the composition. Preferably the solid detergent composition according to the present invention comprises from 0.05 wt.% to 10 wt.% silicone surfactant. Preferably the solid detergent composition comprises at least 0.8 wt.%, preferably at least 0.1 wt.%, still preferably at least 0.15 wt.% and most preferably at least 0.2 wt.%, but typically not more than 4 w.t%, still preferably not more than 3 wt.%, still further preferably not more than 2 wt.% and most preferably not more than 1 wt.%.

Amphoteric surfactant

According to a first aspect of the present invention disclosed composition includes an amphoteric surfactant.
As used herein, the term "amphoteric" includes (a) molecules that contain both an acidic and basic site such as, for example, an amino acid containing both amino (basic) and acid (e.g., carboxylic acid, acidic) functional groups; or (b) zwitterionic molecules which possess both positive and negative charges within the same molecule. The charges of the zwitterionic molecule may be either dependent or independent of the pH of the composition. The term "amphoteric surfactant," as used herein, is also intended to encompass zwitterionic Surfactants, which are well known to formulators skilled in the art as a subset of amphoteric surfactants.
Non-limiting examples of amphoteric surfactants useful in the compositions of the present invention are disclosed in McCutcheon's, Detergents and Emulsifiers, North American edition (1986), published by allured Publishing Corporation; and McCutcheons, Functional Materials, North American Edition (1992); both of which are incorporated by reference herein in their entirety.
Examples of amphoteric surfactants suitable for use in the present invention include, but are not limited to, amphocarboxylates such as alkylamphoacetates (mono or di); alkyl betaines; alkylamidoalkyl betaines; alkylamidoalkyl sultaines; alkylamphophosphates; phosphorylated imidazolines such as phosphobetaines and pyrophosphobetaines; carboxyalkyl alkyl polyamines; alkylimino-dipropionates; alkylamphoglycinates (mono or di); alkylamphoproprionates (mono or di), ); N-alkyl [3-aminoproprionic acids; alkylpolyamino carboxylates; and mixtures thereof.
Specific examples of the amphoteric surfactants include those given hereinbelow.
The amphoteric surfactant is preferably selected from the group consisting of betaines, sultaines, amine oxide or mixtures thereof. A preferred amphoteric surfactant is the betaine type surfactant. Preferably the betaine type amphoteric surfactant has a permanent negative charge and positive charge on the same molecule which does not alter with change in the pH and not having an isoelectric point. They are quaternized derivatives.

Alkyl betaines

where R=C₈-C₃₄ alkyl (saturated or unsaturated) or mixtures thereof. Examples include Coco-Betaine (R=coco alkyl), Lauryl Betaine (R=lauryl, C₁₂H₂₅), and Oleyl Betaine (R=oleyl, C₁₈H₃₅).

Alkylamidoalkyl betaines

where RCO= C₆ to C₂₄ acyl (saturated or unsaturated) or mixtures thereof and x= 1 to 4. Examples include Cocamidoethyl Betaine (RCO=coco acyl, x=2), Cocamidopropyl Betaine (RCO=coco acyl, x=3), Lauramidopropyl Betaine (RCO=lauroyl, and x=3), Myristamidopropyl Betaine (RCO=myristoyl, and x=3), Soyamidopropyl Betaine (R=soy acyl, x=3), and Oleamidopropyl Betaine (RCO=oleoyl, and x=3). Preferably the amphoteric surfactant is Cocamidopropyl Betaine (CAPB). The cocamidopropyl Betaine is commercially available from Rhone-Poulenc as Mirataine BDJ, Galaxy, Huntsman.

Alkyl phosphobetaines

where R=C₆ to C₂₄ alkyl (saturated or unsaturated) or mixtures thereof and M=monovalent cation, such as Sodium Coco PG-Dimonium Chloride Phosphate, where R=coco alkyl and M⁺=Na⁺.

Alkyl sulphobetaines

R¹R²R³⁺NR⁴SO₃ ^-;

where R¹=C₆ to C₂₄ alkyl (saturated or unsaturated) or mixtures thereof and R²and R³, which may be the same or different, are C₁ to C₃ alkyl or hydroxyalkyl groups, for example, methyl groups.

Alkyl Hydroxysultaines

where R=C₈-C₃₄ alkyl (saturated or unsaturated) or mixtures thereof. Examples include Coco-hydroxysultaine (R=coco alkyl) and Lauryl hydroxysultaine (R=lauryl, C₁₂H₂₅).

Alkyl sultaines

where R=C₈-C₃₄ alkyl (saturated or unsaturated) or mixtures thereof. Examples include Coco-sultaine (R=coco alkyl) and Lauryl sultaine (R=lauryl, C₁₂H₂₅).

Alkylamidoalkyl sultaines

where RCO= C₆ to C₂₄ acyl (saturated or unsaturated) or mixtures thereof. Examples include Cocamidopropyl sultaine (RCO=coco acyl, x=3), Lauramidopropyl sultaine (RCO=lauroyl, and x=3), Myristamidopropyl sultaine (RCO=myristoyl, and x=3), soyamidopropyl sultaine (R=soy acyl, x=3), and Oleamidopropyl sultaine (RCO=oleoyl, and x=3).

Alkylamidoalkyl Hydroxysultaines

where RCO= C₆ to C₂₄ acyl (saturated or unsaturated) or mixtures thereof. Examples include Cocoamidopropyl hydroxysultaine (RCO=coco acyl, x=3), Lauramidopropyl hydroxysultaine (RCO=lauroyl, and x=3), Myristamidopropyl hydroxysultaine (RCO=myristoyl, and x=3), Oleamidopropyl hydroxysultaine (RCO=oleoyl, and x=3).
Further useful amphoteric surfactant are those which are broadly described as derivatives of aliphatic secondary and tertiary amines, preferably wherein the nitrogen is in a cationic state, in which the aliphatic radicals can be straight or branched chain and wherein one of the radicals contains an ionizable water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. These amphoteric surfactant includes derivatives of aliphatic amines which contain a long chain of carbon atoms with 8 to 18 carbon atoms and an anionic water-solubilizing group selected from the group consisting of but not limited to carboxylate, sulfonate or sulphate. Examples of the compounds falling within this definition are sodium-3-dodecylamino propane sulfonate and dodecyl dimethyl ammonium hexanoate.

Alkyl amine oxide

R₁R₂R₃N→O

wherein R₁ is typically C₆ to C₂₄ alkyl (saturated or unsaturated) or mixtures thereof. Preferably C₈ to C₁₈ alkyl group, for example, C₁₂ to C₁₄ alkyl. R₂ and R₃, which may be the same or different, are C₁ to C₃ alkyl or hydroxyalkyl groups, for example, methyl groups. Examples include cocamine oxide (R=coco alkyl) and lauramine oxide (RCO = lauryl). The most preferred amine oxide is coco dimethylamine oxide.

Alkylamidoalkyl amine oxide

Where RCO =C₆ to C₂₄ acyl (saturated or unsaturated) or mixtures thereof and x = 1 to 4. Examples include cocamidopropylamine oxide (RCO =coco acyl x =3) and lauramidopropylamine oxide (RCO= lauroyl, x =3), and combinations of two or more thereof.
Preferably the amphoteric surfactant according to the present invention includes those wherein the degree of ionisation varies as a function of pH of the medium it is in. These have an isoelectric point (IEP) in the range from 3.5 to 6.5.
Preferred amphoteric surfactant may also be selected from internally-neutralized derivatives of aliphatic quaternary ammonium and phosphonium and tertiary sulfonium compounds in which the aliphatic radical can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group.
Preferably the amphoteric surfactant is selected from the group consisting of betaines, sultaines, amine oxide, alkyl iminoacetates, imino dialkanoates, amino alkanoates alkyl ammonium propionates, or mixtures thereof. More preferably the amphoteric surfactant are betaines or amine oxide. Preferably the betaine type amphoteric surfactant is selected from alkyl betaines, alkylamidoalkyl betaines and alkyl sulphobetaines. Preferably the amine oxide type amphoteric surfactant is selected from alkyl amine oxide, alkylamidoalkyl amine oxide or mixtures thereof. Most preferably the amphoteric surfactant is a cocamidopropyl betaine (CAPB).
The detergent composition of the present invention includes from 0.2 wt.% to 5 wt.% of an amphoteric surfactant. Preferably the detergent composition comprises at least 0.2 wt.%, still preferably at least 0.3 wt.%, still preferably at least 0.4 wt.%, most preferably at least 0.5 wt.% of the amphoteric surfactant, but typically not more than 4 wt.%, still preferably not more than 3.5 wt.%, still further preferably not more than 3 wt.%, still more preferably not more than 2.5 wt.% and most preferably not more than 1 wt.% of an amphoteric surfactant based on the weight of the detergent composition.
In the solid detergent composition according to the present invention the ratio of the anionic surfactant to the amphoteric surfactant is in a ratio from 0.4:1 to 200:1, still preferably the ratio is from 5:1 to 100:1, In the detergent composition of the present invention the total amount of anionic surfactant is greater than the amphoteric surfactant present in the composition.

Carbonate salt

Disclosed detergent composition includes from 0 wt.% to 20 wt.% carbonate salt. Examples of the carbonate salt includes alkaline earth metal and alkali metal carbonates or mixtures thereof. The carbonate salt is preferably an alkali metal carbonate, alkaline earth metal carbonate or mixtures thereof. Preferred alkali carbonates are sodium and/or potassium carbonate of which sodium carbonate is particularly preferred. It is further preferred that sodium carbonate makes up at least 75 wt.%, more preferably at least 85 wt.% and even more preferably at least 90 wt.% of the total weight of the carbonate salt.
The detergent composition of the present invention includes from 0 wt.% to 20 wt.% carbonate salt. Preferably the detergent composition comprises at least 0.8 wt.%, still preferably at least 1 wt.%, still preferably at least 2 wt.%, most preferably at least 5 wt.% of the carbonate salt, but typically not more than 15 wt.%, still preferably not more than 13 wt.%, most preferably not more than 10 wt.% of carbonate salt based on the weight of the detergent composition. Preferably the composition of the present invention is substantially free of carbonate salt. By substantially free it is meant that there is no deliberately added carbonate salt in the composition.

Non-carbonate builder

In addition to the carbonate salt the detergent composition of the present invention may preferably include a further non-carbonate builder. The preferred inorganic non-carbonate builders may be selected from the group consisting of silicates, silica, zeolites, phosphates or mixtures thereof. Yet other non-carbonate builder may be organic builders which includes but are not limited to as succinates, carboxylates, malonates, polycarboxylates, citric acid or a salt thereof.
Suitable silicates include the water-soluble sodium silicates with an SiO₂: Na₂O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO₂: Na₂O ratio of 2.0 is the most preferred silicate.
Silicates are preferably present in the detergent compositions in accord with the invention at a level from 0 wt.% to 10 wt.% by weight of the composition, more preferably from 0 wt.% to 7 wt.% in the detergent composition.
Preferably the composition of the present invention has low or no phosphate builders such as sodium tripolyphosphate or organic phosphonate sequestrant such as amino trimethylene phosphonic acid sodium salt.
Preferably the composition of the present invention is substantially free of silicate salt, zeolite salt and phosphate builder. By substantially free it is meant that there is no deliberately added carbonate salt in the composition.

Form of the detergent composition

The composition according to the present invention preferably has a pH from 7.0 to 10.5, preferably 7.0 to 10.2, still preferably from 8.5 to 10.2, when measured at 1 wt.% dilution in de-ionised water at 25°C. The composition may preferably include a buffer.
The composition of the present invention is in the solid form. The composition according to the present invention may be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying. The detergent composition may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying.
The compositions herein can take a variety of physical solid forms including forms such as powder, granule, ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet, still preferably the composition is in the form of a powder. The composition may be in the form of a unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. The composition according to the present invention may preferably be in a form selected from powder, unit dose or pouch form, tablet, bar, or flake.
The solid laundry detergent composition according to the present invention is preferably free flowing. The composition is preferably a fully formulated detergent composition. The solid detergent composition includes but is not limited powder, granular, particulate, agglomerates, noodles, flakes tablets, bar, sheet or other solid forms known in the art and combinations thereof.
Preferably the composition is for manual-washing. Preferably, the composition of the present invention is a solid laundry detergent composition. Preferably the composition is in the form of a spray -dried powder or particulate free-flowing form.
The compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
The solid laundry detergent composition according to the present invention preferably has from 0 wt.% to 8 wt.% zeolite builder. Preferably the amount of zeolite builder is less than 5 wt.%, still preferably less than 3 wt.%, more preferably less than 2 wt.% by weight in the detergent composition and most preferably the detergent composition is substantially free of zeolite builder.
The solid laundry detergent composition according to the present invention preferably has from 0 wt.% to 4 wt.% phosphate builder. Preferably the amount of phosphate builder is less than 3 wt.%, still preferably less than 2 wt.%, more preferably less than 1 wt.% by weight in the detergent composition and most preferably the detergent composition is substantially free of phosphate builder.
The solid laundry detergent composition according to the present invention preferably includes from 0 wt.% to 6 wt.% bicarbonate salt, preferably sodium bicarbonate. Preferably the amount of bicarbonate salt is less than 5 wt.%, still preferably less than 2 wt.%, more preferably less than 1 wt.% by weight in the detergent composition and most preferably the detergent composition is substantially free of bicarbonate salt. Preferably the bicarbonate salt is sodium bicarbonate.
The term "substantially free" means that the indicated component is at the very minimum, not deliberately added to the composition to form part of it, or, more typically, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included.

Optional ingredients

The detergent composition of the present invention may preferably include one or more of the optional ingredients selected from the group consisting of cleaning and care ingredients. The optional ingredients include one or more adjunct cleaning additives selected from polymers, enzymes, enzyme stabilizer, brightening agents, hueing agent, bleach, chelating agent, humectant, perfume, filler or carrier, an alkalinity system, a buffer or combinations thereof.

Polymers:

The composition of the present invention may preferably include polymers which provide cleaning or care benefits. The cleaning polymer includes but is not limited to soil release polymer, carboxylate polymers, antiredeposition polymers, cellulosic polymers, care polymers, amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil suspending polymers or mixtures thereof.
Suitable carboxylate polymer includes polymers such as a maleate/acrylate random copolymer or polyacrylate homopolymer. Also suitable are polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid, copolymer of maleic acid with vinyl methyl ether and combinations thereof.
Anti-redeposition polymers are designed to suspend or disperse soil. Typically, antiredeposition polymers are polyethylene glycol polymers, polycarboxylate polymers, polyethyleneimine polymers or mixtures thereof. Such polymers are available from BASF under the trade name Sokalan^®CP5 (neutralised form) and Sokalan^®CP45 (acidic form).
Soil release polymers are designed to modify the surface of the fabric to facilitate the ease of removal of soil. Suitable soil release polymers are sold by Clariant under the TexCare^® series of polymers, e.g. TexCare^® SRN240, TexCare^® SRN100, TexCare^® SRN170, TexCare^® SRN300, TexCare^® SRN325, TexCare^® SRA100 and TexCare^® SRA300. Other suitable soil release polymers are sold by Rhodia under the Repel-o-Tex@ series of polymers, e.g. Repel-o-Tex^® SF2, Repel-o-Tex^® SRP6 and Repel-o-Tex@ Crystal. A preferred polymer is selected from the group consisting of polyester soil release polymer, both end-capped and non-end-capped sulphonated PET/POET polymers, both end-capped and non-end-capped unsulphonated PET/POET polymers or combinations thereof.
Preferably the levels of these soil release polymer in the adjunct particle is from 3 wt.% to 15 wt.% at least 5 wt.%, still preferably at least 6 wt.%, still preferably at least 6.5 wt.%, most preferably at least 7 wt.%, but typically not more than 14 wt.%, still preferably not more than 13 wt.%, most preferably not more than 12 wt.%.
Suitable care polymers include cellulosic polymers that are cationically modified or hydrophobically modified. A suitable commercially available dye lock polymer is Polyquart^® FDI (Cognis). Preferably the adjunct particle includes from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of care polymer.
Examples of suitable sequestering polymers are DEQUEST^™, organic phosphonate type sequestering polymers sold by Monsanto and alkanehydroxy phosphonates. The cleaning composition is preferably substantially free of phosphate based sequestering polymers. By substantially free, it is meant herein that no phosphate based sequestering polymers is deliberately added.

Enzymes:

The composition of the present invention preferably includes an enzyme. It may preferably include one or more enzymes. Preferred examples of the enzymes include those which provide cleaning performance and/or fabric care benefits.
Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, xyloglucanase, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, G-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with one or more of amylase, mannanase and cellulase. When present in a detergent composition, the enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001 % to about 1% or from 0.001 % to about 0.5% enzyme protein by weight of the detergent composition.
Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable commercially available protease enzymes include those sold under the trade names Alcalase^®, Savinase^®, Primase^®, Durazym^®, Polarzyme^®, Kannase^®, Liquanase^®, Liquanase Ultra^®, Savinase Ultra^®, Ovozyme^®, Neutrase^®, Everlase^® and Esperase^® by Novozymes A/S (Denmark), those sold under the tradename Maxatase^®, Maxaca^®l, Maxapem^®, Properase^®, Purafect^®, Purafect Prime^®, Purafect Ox^®, FN3^®, FN4^®, 10 Excellase^® and Purafect OXP^® by Genencor International, those sold under the tradename Opticlean^® and Optimase by Solvay Enzymes.
Suitable alpha-amylases include those of bacterial or fungal origin. Suitable commercially available alpha-amylases include DURAMYL^®, LIQUEZYME^®, TERMAMYL^®, TERMAMYL ULTRA^®, NATALASE^®, SUPRAMYL^®, STAINZYME^®, STAINZYME PLUS^®, FUNGAMYL^® and BAN^® (Novozymes A/S, Bagsvaerd, Denmark), 15 KEMZYM^® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE^®, PURASTAR^®, ENZYSIZE^®, OPTISIZE HT PLUS^®, POWERASE^® and PURASTAR OXAM^® (Genencor International Inc., Palo Alto, California) and KAM^® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210,Japan). In one aspect, suitable amylases include NATALASE^®, STAINZYME and STAINZYME PLUS^® and mixtures thereof.
In one aspect, such enzymes may be selected from the group consisting of: lipases, including "first cycle lipases". Preferred lipases would include those sold under the tradenames Lipex^® and Lipolex^®.
In one aspect, other preferred enzymes include microbial-derived endoglucanases exhibiting endo-beta-1, 4-glucanase activity (E.C. 3.2.L4), including a bacterial polypeptide. Suitable endoglucanases are sold under the tradenames Celluclean^® and Whitezyme^® (Novozymes A/S, Bagsvaerd, Denmark). Other preferred enzymes include pectate lyases sold under the tradenames Pectawash^®, Pectaway^®, Xpect^® and mannanases sold under the tradenames Mannaway^® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite^® (Genencor International Inc., Palo Alto, California).

Enzyme stabilizing system:

The enzyme-containing compositions described herein may optionally comprise from 0.001 % to 10%, in some examples from about 0.005% to about 8%, and in other examples, from about 0.01 % to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can, for example, comprise calcium ion, propylene glycol, short chain carboxylic acids, chlorine bleach scavengers and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the cleaning composition.

Brightening agents:

Optical brighteners or other brightening or whitening agents may be incorporated at levels from 0.01 % to 1.2%, by weight of the composition. Commercial brighteners suitable for the present invention can be classified into subgroups, including but not limited to: derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinecyanines, dibenzothiophene-5, 5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Preferred commercially available Brighteners includes Tinopal AMS-GX by Ciba Geigy Corporation, Tinopal UNPA-GX by Ciba-Geigy Corporation, Tinopal 5BM-GX by Ciba-Geigy Corporation. The brighteners may be added in particulate form or as a premix with a suitable solvent, for example nonionic surfactant, monoethanolamine, propane diol.

Fabric hueing agents:

The composition may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically, the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments.
According to a second aspect of the present invention disclosed is a method of laundering a textile surface with the detergent composition according to the first aspect comprising the steps of: (i) preparing a wash liquor by mixing the detergent composition according to the first aspect with a liquid, preferably water; (ii) soaking said textile surface in the wash liquor for a predetermined period of time; and, optionally rinsing the textile surface.
According to a third aspect of the present invention disclosed is a use of an anionic surfactant, amphoteric surfactant and a silicone surfactant in a detergent composition comprising from 0 wt.% to 20 wt.% carbonate salt and 0 wt.% to 10 wt.% silicate salt to provide improved stain removal performance.

Examples

A spray-dried solid laundry detergent composition according to the present invention was prepared with the formulation as shown in table 1 below.

Table 1

Ingredients	Ex 1
Anionic surfactant	19.78
Amphoteric surfactant (CAPB)	0.5
Silicone surfactant	1.0
Sodium silicate	7.66
Sodium carbonate	9.2
Layering agent	6.71
Antifoam agent
Speckles	0.5
Perfume	0.36
Moisture, salt, NDOM and other minor ingredients	2.19
Sodium sulphate filler	Upto 100

The composition according to the present invention (Ex 1 ) in table 1 includes an anionic surfactant, amphoteric surfactant and a silicone surfactant in presence of low levels of the carbonate and provides good stain removal performance.

Claims

A solid laundry detergent composition comprising:
i) anionic surfactant;

ii) a silicone surfactant;

iii) an amphoteric surfactant;

iv) 0 wt.% to 20 wt.% carbonate; and,

v) 0 wt.% to 10 wt.% silicate salt.
A solid laundry detergent composition according to claim 1 wherein the silicone surfactant is selected from the group consisting of:
i) a polydialkyl siloxane surfactant having the general formula (I), (II) or mixtures thereof,

where PE represent a non-ionic group and is represented by the formula (a)

-CH₂-(CH₂)_p-O-(EO)_m(PO)_n-Z, ...... (a)

wherein EO representing ethylene oxide, PO representing propylene oxide, "x" is a number that ranges from about 0 to about 100, "y" is a number that ranges from about 1 to 100, "m", "n" and "p" are numbers that range from 0 to 50, m+n ≥ 1 and Z represents hydrogen or R wherein each R independently represents a lower (C₁ to C₆) straight or branched alkyl or PE is represented by formula (b)
or PE is represented by formula (c)
Or,

ii) a silicone surfactant having the general formula (III)
where, PA= -(C₂H₄O) _a (C₃H₆O) _b R or
and wherein "x" represent a number that ranges from 0 to 100, preferably x is 0 or 1 and "y" represent a number that ranges from 1 to 100, preferably y is at least 1. "a" and "b" represent numbers that independently range from 0 to 60, a+b≥1, and each R is independently H or a lower straight or branched (C₁ to C₆) alkyl;
Or,

iii) an end-blocked (AEB type) silicone surfactant represented by the general formula (IV):

R=-(CH₂)₃-O-(C₂H₄O)_x(C₃H₆O)_y-H

wherein x represents 0 to 100, y represents 1 to 100, x + y represents 1 to 200;
Or,

iv) a trisiloxane surfactant represented by the general formula (V) or (VI)
wherein R₁ and R₂ are each independently an alkyl having 1 to 3 carbon atoms or C_nH_2nO[C₂H₄O]_y [C₃H₆O]_z Q provided R₁ and R₂ are not the same, "a" is 0 to 2, "n" has a value from 2 to 4; "y" has a value of 3 to 10; "z" has a value from 0 to 5; Q is selected from the group consisting of hydrogen and a branched or straight chain alkyl having 1 to 4 carbon atoms where preferably "a" is 0 to 1, "n" is 2 to 4, "y" is 5 to 9, "z" is 0 to 3 and "Q" is a 1 to 3 straight alkyl;
wherein n= 2 to 4, y= 3 to 10, z= 0 to 5, and where R is either an alkyl having 1-4 carbon atoms or R is an OH or H group, provided that when z = 0, R = H and when z = 1 to 5 R = OH or )-alkyl having 1 to 4 carbon atoms and combinations thereof.
A composition according to any one of the preceding claims wherein the amphoteric surfactant is selected from the group consisting of betaines, sultaines, amine oxide or mixtures thereof.
A composition according to claim 3 wherein the betaine amphoteric surfactant is selected from alkyl betaines, alkylamidoalkyl betaines, alkyl phosphobetaines, alkyl sulphobetaines or mixtures thereof.
A composition according to any one of the preceding claims wherein the anionic surfactant is selected from the group consisting alkyl sulphate, alkyl sulphonate, alkyl ether sulphonate or combinations thereof, preferably the anionic surfactant is an alkali metal salt of C₁₀ to C₁₈ alkyl benzene sulfonic acid.
A composition according to any one of the preceding claims wherein the composition at 1 wt.% dilution in deionized water at 25°C, has an equilibrium pH in the range from 7.0 to 10.5.
A composition according to any one of the preceding claims wherein the amount of anionic surfactant is from 2 wt.% to 40 wt.% of the composition.
A composition according to any one of the preceding claims wherein the amount of amphoteric surfactant is from 0.2 wt.% to 5 wt.% of the composition.
A composition according to any one of the preceding claims wherein the amount of silicone surfactant is from 0.1 wt.% to 10 wt.% of the composition.
A composition according to any one of the preceding claims wherein the composition comprises an antiredeposition agent preferably selected from the group consisting of polyacrylates, copolymer of acrylic acid or methacrylic acid with maleic acid or maleic acid with vinyl ester and combinations thereof.
A composition according to any one of the preceding claims wherein the composition comprises an enzyme.
A composition according to any one of the preceding claims wherein the composition comprises a whitening agent selected from the group consisting of dyes, pigments, fluorescers or combinations thereof.
A method of laundering a textile surface with the detergent composition according to any one of the preceding claims comprising the steps of:
i) preparing a wash liquor by mixing the detergent composition according to any one of the preceding claims with a liquid, preferably water;

ii) soaking said textile surface in the wash liquor for a predetermined period of time; and,

iii) optionally rinsing the textile surface.
Use of an anionic surfactant, amphoteric surfactant and a silicone surfactant in a detergent composition comprising from 0 wt.% to 20 wt.% carbonate salt and 0 wt.% to 10 wt.% silicate salt to provide improved stain removal performance.