阅读说明：本技术 洗涤剂组合物 (Detergent composition ) 是由 S·N·巴切洛尔 N·S·伯纳曼 A·T·库克 D·A·兰 于 2019-09-12 设计创作，主要内容包括：本发明涉及一种洗涤剂组合物,其包含：a)2至95重量％,优选2至50重量％,更优选2至40重量％,最优选2.5至40重量％的形式(I)的单甘油酯和二甘油酯的有机酸衍生物：其中R-1、R-2和R-3中的一个或两个独立地选自式R-4CO-的酰基；其中R-4是直链或支链的、饱和或单不饱和的C-9至C-(21)烷基链；其中R-1、R-2和R-3中的一个或两个选自通式(HOOC)-nXCO-的有机酸；其中X是含有1至6个碳原子的饱和或单不饱和有机基团,并且n＝1-3；其中R-1、R-2和R-3中的一个或没有任何一个选自H；和b)0.0005至0.5重量％,优选0.005至0.2重量％的脂质酯酶；和使用所述组合物处理织物的家用方法。(The present invention relates to a detergent composition comprising: a) from 2 to 95% by weight, preferably from 2 to 50% by weight, more preferably from 2 to 40% by weight, most preferably from 2.5 to 40% by weight, of organic acid derivatives of mono-and diglycerides of form (I): wherein R is 1 、R 2 And R 3 One or two of which are independently selected from the formula R 4 Acyl of CO-; wherein R is 4 Is straight-chain or branched, saturated or monounsaturated C 9 To C 21 An alkyl chain; wherein R is 1 、R 2 And R 3 One or two of which are selected from the general formula (HOOC) n Organic acids of XCO-; wherein X is a saturated or monounsaturated organic group containing 1 to 6 carbon atoms, and n ═ 1-3; wherein R is 1 、R 2 And R 3 One or none of (a) is selected from H; and b)0.0005 to 0.5 wt.%, preferably 0.005 to 0.2 wt.% of a lipid esterase; and a domestic method of treating fabrics using the composition.)

1. A detergent composition comprising:

a) from 2 to 95% by weight, preferably from 2 to 50% by weight, more preferably from 2 to 40% by weight, most preferably from 2.5 to 40% by weight, of organic acid derivatives of mono-and diglycerides in the form: -

Wherein R is₁、R₂And R₃One or two of which are independently selected from the formula R₄Acyl of CO-; wherein R is₄Is straight-chain or branched, saturated or monounsaturated C₉To C₂₁An alkyl chain; wherein R is₁、R₂And R₃One or two of which are selected from the general formula (HOOC)_nOrganic acids of XCO-; wherein X is a saturated or monounsaturated organic group containing 1 to 6 carbon atoms, and n-1-3;

wherein R is₁、R₂And R₃One or none of (a) is selected from H; and

b)0.0005 to 0.5 wt.%, preferably 0.005 to 0.2 wt.% of a lipid esterase.

2. The detergent composition of claim 1, wherein R₁、R₂And R₃Is independently selected from the formula R₄Acyl of CO-, wherein R₄Is straight-chain or branched, saturated or monounsaturated C₉To C₂₁An alkyl chain.

3. The detergent composition according to claim 1 or claim 2, wherein R is₄Is straight-chain or branched, saturated or monounsaturated C₁₅To C₂₁Linear alkyl chain, preferably saturated or monounsaturated C₁₅To C₁₇A linear alkyl chain.

4. The detergent composition according to any preceding claims, wherein R₁、R₂And R₃One of them is selected from the general formula (HOOC)_nOrganic acids of XCO-; wherein X is a saturated or monounsaturated organic group containing 1 to 6 carbon atoms, and n-1-3。

5. The detergent composition according to any preceding claims, wherein (HOOC)_nXCO is selected from citric acid, malic acid, tartaric acid, monoacetyl and diacetyl tartaric acid, succinic acid, oxalic acid, maleic acid, fumaric acid, malonic acid, more preferably citric acid, lactic acid, tartaric acid, monoacetyl and diacetyl tartaric acid, wherein the acid groups lose OH to form esters.

6. The detergent composition according to any preceding claims, wherein R₁、R₂And R₃Is selected from H.

7. The detergent composition according to any preceding claims, wherein the organic acid derivative of mono-and diglycerides is selected from the group consisting of: citric acid esters of mono-and diglycerides (citrem); tartaric acid esters of mono-and diglycerides (tatem); diacetyl tartaric acid esters of mono-and diglycerides (datem); and mixed acetic, tartaric and diacetylated tartaric acid esters of mono-and diglycerides (MATEM); preferably, the organic acid derivatives of mono-and diglycerides are selected from: citric acid esters of mono-and diglycerides (citrem); tartaric acid esters of mono-and diglycerides (tatem); and diacetyl tartaric acid esters of mono-and diglycerides (datem); most preferably, the organic acid derivatives of mono-and diglycerides are selected from the group consisting of: citric acid esters of mono-and diglycerides (citrem).

8. The detergent composition according to any preceding claims, wherein the detergent composition is a laundry detergent composition.

9. The detergent composition according to claim 8, comprising a nonionic surfactant selected from the group consisting of saturated and monounsaturated fatty alcohol ethoxylates and saturated and monounsaturated fatty acid sugar esters; preferably, said is notThe ionic surfactants are saturated and monounsaturated fatty alcohol ethoxylates, preferably selected from the group consisting of C having an average of 5 to 30 ethoxylates₁₂To C₂₀Linear primary alcohol ethoxylates, more preferably C having an average of 10 to 25 ethoxylates₁₆To C₁₈A linear primary alcohol ethoxylate.

10. A laundry detergent composition according to claim 8 or claim 9 comprising a surfactant selected from C₁₂To C₁₈Alkyl ether carboxylates and water-soluble alkali metal salts of organic sulfuric, ether sulfuric and sulfonic acids having alkyl groups containing from 8 to 22 carbon atoms.

11. A laundry detergent composition according to any preceding claims, wherein the lipid esterase is selected from the group consisting of triacylglycerol lipases (e.c. 3.1.1.3); carboxylic ester hydrolases (e.c. 3.1.1.1); cutinase (e.c. 3.1.1.74); sterol esterase (e.c. 3.1.1.13); wax ester hydrolase (e.c.3.1.1.50), preferably triacylglycerol lipase (e.c. 3.1.1.3).

12. A laundry detergent composition according to any of claims 8 to 10 comprising one or more enzymes selected from protease, amylase and cellulase.

13. A laundry detergent composition according to any one of claims 8 to 12, wherein the composition is a liquid or liquid unit dose composition.

14. A domestic method of treating a fabric comprising the steps of:

a) treating a fabric with from 0.5 to 20g/L, more preferably from 1 to 10g/L of an aqueous solution of the detergent composition according to any of claims 1 to 13;

b) optionally rinsing and drying the fabric.

Technical Field

The present invention relates to detergent compositions. More particularly, detergent compositions comprising surfactants which are organic acid derivatives of mono-and diglycerides and a lipase (lipid esterase).

Background

Organic acid ester derivatives of mono-and diglycerides are surfactants used in food processing, for example in bakeries to improve bread quality or in chocolate to prevent bloom. They are produced from animal and plant based ingredients.

Detergents typically include lipases that hydrolyze fats. Surfactants are used in detergents to solubilize fats. However, it was found that conventional surfactants can adversely affect lipases. It would be desirable to find surfactants that do not have this adverse effect on lipases, and thus improve lipase performance.

Disclosure of Invention

In a first aspect, the present invention relates to a detergent composition comprising:

a) from 2 to 95% by weight, preferably from 2 to 50% by weight, more preferably from 2 to 40% by weight, most preferably from 2.5 to 40% by weight, of organic acid derivatives of mono-and diglycerides in the form: -

Wherein R is₁、R₂And R₃One or two, preferably one, of the groups are independently selected from the formula R₄Acyl of CO-, wherein R₄Is straight-chain or branched, saturated or monounsaturated C₉To C₂₁Alkyl chain, preferably C₁₅To C₂₁Straight alkyl chain, most preferably saturated or monounsaturated C₁₅To C₁₇A linear alkyl chain;

wherein R is₁、R₂And R₃One or two, preferably one, of the compounds of the formula (HOOC)_nAn organic acid of XCO-, wherein X is a saturated or monounsaturated organic group containing 1 to 6 carbon atoms, and n ═ 1-3;

wherein R is₁、R₂And R₃One or none of them is selected from H, preferably R₁、R₂And R₃One of which is selected from H; and

b)0.0005 to 0.5 wt.%, preferably 0.005 to 0.2 wt.% of a lipid esterase.

In a second aspect, the present invention provides a domestic method of treating a fabric, the method comprising the steps of:

a) treating the fabric with from 0.5 to 20g/L, more preferably from 1 to 10g/L, of an aqueous solution of the detergent composition according to the first aspect of the invention;

b) optionally rinsing and drying the fabric.

Preferably, wherein (HOOC)_nXCO is selected from citric acid, malic acid, tartaric acid, monoacetyl and diacetyl tartaric acid, succinic acid, oxalic acid, maleic acid, fumaric acid, malonic acid, more preferably citric acid, lactic acid, tartaric acid, monoacetyl and diacetyl tartaric acid, wherein the acid groups lose OH to form esters.

Preferably, the organic acid derivatives of mono-and diglycerides are selected from: citric acid esters of mono-and diglycerides (citrem); tartaric acid esters of mono-and diglycerides (tatem); diacetyl tartaric acid esters of mono-and diglycerides (datem); and mixed acetic, tartaric, and diacetylated tartaric acid esters of mono-and diglycerides (MATEM); preferably, the organic acid derivatives of mono-and diglycerides are selected from: citric acid esters of mono-and diglycerides (citrem).

Preferably, the detergent composition is a laundry detergent composition.

Preferably, the laundry detergent composition comprises a surfactant selected from C₁₂To C₁₈Alkyl ether carboxylates and water-soluble alkali metal salts of organic sulfuric, ether sulfuric, and sulfonic acids having alkyl groups containing from about 8 to about 22 carbon atoms.

Preferably, the lipid esterase is selected from the group consisting of triacylglycerol lipases (e.c. 3.1.1.3); carboxylic ester hydrolases (e.c. 3.1.1.1); cutinase (e.c. 3.1.1.74); sterol esterase (e.c. 3.1.1.13); wax ester hydrolase (e.c.3.1.1.50), preferably triacylglycerol lipase (e.c. 3.1.1.3).

Preferably, the laundry detergent composition comprises one or more enzymes selected from the group consisting of proteases, amylases and cellulases.

Preferably, the composition is a liquid or liquid unit dose composition.

Detailed Description

The formulation may be in any form, e.g., liquid, solid, powder, liquid unit dose.

Preferably, the composition is a liquid or liquid unit dose composition.

When dissolved in demineralized water, the formulation preferably has a pH of 4 to 8, more preferably 6.5 to 7.5, most preferably 7.

Organic acid derivatives of mono-and diglycerides

Organic acid derivatives of mono-and diglycerides are referred to herein as glycerol carboxylates.

Organic acid derivatives of mono-and diglycerides have the following form: -

Wherein R is₁、R₂And R₃One or two, preferably one, of the groups are independently selected from the formula R₄Acyl of CO-, wherein R₄Is straight-chain or branched, saturated or monounsaturated C₉To C₂₁Alkyl chain, preferably C₁₅To C₂₁Straight alkyl chain, most preferably saturated or monounsaturated C₁₅To C₁₇A linear alkyl chain;

wherein R is₁、R₂And R₃One or two, preferably one, of the compounds of the formula (HOOC)_nAn organic acid of XCO-, wherein X is a saturated or monounsaturated organic group containing 1 to 6 carbon atoms, and n ═ 1-3;

wherein R is₁、R₂And R₃One or none of them is selected from H, preferably R₁、R₂And R₃Is selected from H.

Preferably, (HOOC)_nXCO is selected from citric acid, malic acid, tartaric acid, monoacetyl and diacetyl tartaric acid, succinic acid, oxalic acid, maleic acid, fumaric acid, malonic acid, more preferably citric acid, lactic acid, tartaric acid, monoacetyl and diacetyl tartaric acid, wherein the acid groups lose OH to form esters.

The weight of the organic acid derivatives of monoglycerides and diglycerides is in protonated form.

The carboxylic acid glycerides may be synthesized by esterifying monoglycerides and diglycerides with organic acids. Mono-and diglycerides can be produced by fat glycerolysis (200 ℃, basic catalyst). The monoglycerides may be separated by distillation under high vacuum. Mono-and diglycerides can also be produced by lipid esterase catalyzed hydrolysis of fats. The organic acid may then be added by esterification or reaction with the anhydride of the organic acid (when the structure allows).

The nature and synthesis of glycerides of carboxylic acids are discussed in Food Emulsifiers and therir application.2008(Springer) by Hasenhuettl, g.l and Hartel, R.W, (eds) and Emulsifiers in Food Technology 2008(Wiley-VCH) by Whitehurst, R.J (eds) and in version 2 2015 of this book (Wiley-Blackwell) by v.norn.

Preferred organic acid derivatives of mono-and diglycerides are selected from the group consisting of:

e472c citric acid esters of mono-and diglycerides (citrem);

e472d tartaric acid esters of mono-and diglycerides (tatem);

E472E diacetyl tartaric acid ester of mono-and diglycerides (datem); and

e472f mixed acetic, tartaric and diacetylated tartaric acid esters of mono-and diglycerides (MATEM).

More preferred organic acid derivatives of mono-and diglycerides are selected from:

e472c citric acid esters of mono-and diglycerides (citrem);

e472d tartaric acid esters of mono-and diglycerides (tatem); and the combination of (a) and (b),

E472E diacetyl tartaric acid ester of mono-and diglycerides (datem).

Wherein the E number is the code of substances allowed to be used as food additives within the european union.

E472c citric acid esters of mono-and diglycerides (citrem) are most preferred.

Preferably, the glycerol carboxylate is an acid ester of a monoglyceride. Preferably, the monoglycerides are obtained from plants, preferably from rapeseed, sunflower, corn (maze), soybean, peanut, cottonseed, olive oil, tall oil.

The glycerol carboxylates may be in salt or acid form, usually water-soluble sodium, potassium, ammonium, magnesium or mono-, di-or tri-C₂-C₃In the form of an alkanolammonium salt, where sodium cation is a common choice.

Preferably, the glycerol carboxylates have predominantly saturated and monounsaturated C₁₈Linear alkyl chain, most preferablySelecting (C)₁₈Carboxylic acid glyceride)/(C₁₆Glycerol carboxylate) is preferably from 2 to 400, more preferably from 8 to 200, wherein the weight of glycerol carboxylate is in protonated form.

Examples of preferred structures are

These are saturated C₁₈A carboxylic acid glyceride.

Preferably, the glycerol carboxylate ester comprises less than 1 wt% of material having polyunsaturated alkyl chains, more preferably less than 0.5 wt%, most preferably less than 0.1 wt%. This can be obtained by hydrogenation of the oil.

Carboxylic acid glycerides are available from Danisco, Palsgaard and Acaris.

The organic acid derivatives of mono-and diglycerides are present at a level of 1 to 95% by weight, preferably 1.5 to 50% by weight, more preferably 2 to 40% by weight. Other preferred levels include from 2.5 to 95 wt%, preferably from 2.5 to 50 wt%, more preferably from 2.5 to 40 wt%. Other preferred levels include 3 to 95 wt%, preferably 3 to 50 wt%, more preferably 3 to 40 wt%.

The glycerol carboxylates are often provided as unsubstituted mono-and diglycerides, preferably the weight ratio (glycerol carboxylate)/(unsubstituted mono-and diglycerides) is greater than 1, more preferably greater than 2, most preferably greater than 4. Preferably, the unsubstituted monoglycerides and diglycerides are predominantly monoglycerides by weight.

Lipid esterase

Cleaning lipid esterases are discussed in Enzymes in detergents (1997Marcel Dekker, New York) by Jan H.Van Ee, Ono Misset and Erik J.Baas.

The detergent lipid esterases are preferably active at alkaline pH in the range of 7 to 11, most preferably they have maximum activity at pH in the range of 8 to 10.5.

The lipid esterase may be selected from lipases in e.c. class 3.1 or 3.2 or a combination thereof.

Preferably, the detergent lipid esterase is selected from the group consisting of:

(1) triacylglycerol lipase (E.C.3.1.1.3)

(2) Carboxylic ester hydrolase (E.C.3.1.1.1)

(3) Cutinase (E.C.3.1.1.74)

(4) Sterol esterase (E.C.3.1.1.13)

(5) Wax ester hydrolase (E.C.3.1.1.50)

Triacylglycerol lipases (e.c.3.1.1.3) are most preferred.

Suitable triacylglycerol lipases can be selected from the group of variants of Humicola lanuginosa (Humicola lanuginosa) (Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases may be selected from variants of Pseudomonas lipases, for example from Pseudomonas alcaligenes (P.alcaligenes) or Pseudomonas pseudoalcaligenes (EP218272), Pseudomonas cepacia (P.cepacia) (EP331376), Pseudomonas stutzeri (GB1,372,034), Pseudomonas fluorescens (P.fluorosceens), Pseudomonas sp.SD 705(WO95/06720 and WO96/27002), Pseudomonas wisconsinensis (P.wisconsinensis) (WO 96/12012); variants of Bacillus lipases, for example from Bacillus subtilis (B.subtilis) (Dartois et al (1993), Biochemica et Biophysica Acta, 1131, 253-doped bacteria 360), Bacillus stearothermophilus (B.stearothermophilus) (JP64/744992) or Bacillus pumilus (B.pumilus) (WO 91/16422).

Suitable carboxylic ester hydrolases may be selected from the wild-type or variants of carboxylic ester hydrolases endogenous to Burkholderia gladioli (B.gladioli), Pseudomonas fluorescens, Pseudomonas putida, Bacillus acidocaldarius (B.acidocaldarius), Bacillus subtilis, Bacillus stearothermophilus, Streptomyces aureolantus (Streptomyces chrysogenus), Streptomyces diastatochromogenes (S.diastatochromogenes) and Saccharomyces cerevisiae.

Suitable cutinases may be selected from wild-type or variants of cutinases endogenous to the following strains: a strain of aspergillus, in particular aspergillus oryzae; strains of the genus Alternaria, in particular Alternaria brassiciola; strains of the genus Fusarium, in particular Fusarium solani, Fusarium solani pisi (Fusarium solani pisi), Fusarium oxysporum, Fusarium cepacium (Fusarium oxysporum cepa), Fusarium culmorum or Fusarium roseum (Fusarium roseum sambucium); strains of the genus Helminthosporium, in particular Helminthosporium sativum; a strain of the genus humicola, in particular humicola insolens; a strain of the genus Pseudomonas, in particular Pseudomonas mendocina or Pseudomonas putida; a strain of the genus rhizoctonia, in particular rhizoctonia solani; strains of the genus streptomyces, in particular streptomyces scabies; a strain of Coprinus, in particular Coprinus cinereus; a strain of the genus Thermobifida, in particular Thermobifida fusca; a strain of the genus calophyllum giganteum (Magnaporthe), in particular calophyllum giganteum (Magnaporthe grisea); or a strain of the genus Geobacillus, in particular Geobacillus grandis (Ulocladium consortiale).

In a preferred embodiment, the cutinase is selected from the group consisting of variants of Pseudomonas mendocina cutinase described in WO2003/076580(Genencor), such as variants having three substitutions at I178M, F180V and S205G.

In another preferred embodiment, the cutinase is a wild-type or variant of six cutinases endogenous to Coprinus cinereus as described in H.Kontkanen et al, App.environ.microbiology, 2009, pp.2148-2157.

In another preferred embodiment, the cutinase is a wild type or variant of two cutinases endogenous to trichoderma reesei as described in WO2009007510 (VTT).

In a most preferred embodiment, the cutinase is derived from a strain of humicola insolens, in particular the humicola insolens strain DSM 1800. Specific Humicola cutinases are described in WO96/13580, which is incorporated herein by reference. The cutinase may be a variant, for example one of the variants disclosed in WO00/34450 and WO 01/92502. Preferred cutinase variants include those listed in example 2 of WO 01/92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

Suitable sterol esterases may be derived from strains of the genus Ophiostoma (Ophiostoma), such as spruce Ophiostoma piceae; strains of the genus pseudomonas, such as pseudomonas aeruginosa; or a strain of Melanocarpus, for example Melanocarpus albomyces.

In a most preferred embodiment, the sterol esterase is a Melanocarpus albomyces sterol esterase described in H.Kontkanen et al, Enzyme Microb technol., 39, (2006), 265- & 273.

Suitable wax ester hydrolases may be derived from jojoba (Simmondsia chinensis), california.

The lipid esterase is most preferably selected from the group consisting of lipid enzymes in e.c. class 3.1.1.1 or 3.1.1.3 or combinations thereof, most preferably e.c. 3.1.1.3.

Examples of EC3.1.1.3 lipases include those described in WIPO publications WO00/60063, WO99/42566, WO02/062973, WO97/04078, WO97/04079 and US5,869,438. Preferred lipases are produced by: absidia reflexa (Absidia reflexa), Absidia umbellata (Absidia corembefer), Rhizomucor miehei (Rhizmucor miehei), Rhizopus deleman, Aspergillus niger, Aspergillus tubingensis (Aspergillus tubigensis), Fusarium oxysporum (Fusarium oxysporum) ((Absida))oxysporum), Fusarium heterosporum (Fusarium heterotroporum), Aspergillus oryzae (Aspergillus oryzae), penicillium camembertii (penicillium camembertii), Aspergillus foetidus (Aspergillus foetidus), Aspergillus niger, Thermomyces lanuginosus (Thermomyces lanogenus) (synonyms: humicola lanuginosa) and Landerina penicillapora, in particular Thermomyces lanuginosus. Certain preferred lipases are those sold under the trade name NovozymesLipolaseAnd(registration of NovozymesTrademark) offering; and LIPASE PAvailable from Areario Pharmaceutical co.ltd., famous ancient houses, japan;commercially available from Toyo Jozo co., Tagata, japan; and additional chromobacterium viscosum (chromobacterium viscosum) lipase from Amersham Pharmacia biotech, Piscataway, new jersey, usa and Diosynth co, netherlands; and other lipases, such as Pseudomonas gladioli (Pseudomonas gladioli). Further useful lipases are described in WIPO publications WO02062973, WO2004/101759, WO2004/101760 and WO 2004/101763. In one embodiment, suitable lipases include the "first cycle lipase" described in WO00/60063 and us patent 6,939,702B1, preferably a variant of SEQ ID No.2, more preferably a variant of SEQ ID No.2 having at least 90% homology to SEQ ID No.2, comprising replacement of the neutral or negatively charged amino acid at any of positions 3, 224, 229, 231 and 233 by R or K, most preferably a variant comprising a T231R and N233R mutation, such most preferred variants being under the trade name "first cycle lipase", such variants being preferred(Novozymes).

The above lipases may be used in combination (any mixture of lipases may be used). Suitable lipases are commercially available from Novozymes, Bagsvaerd, denmark; areario Pharmaceutical Co.Ltd., famous ancient houses, Japan; toyo Jozo co., Tagata, japan; amersham Pharmacia biotech, Piscataway, new jersey, usa; dios, netherlands; and/or prepared according to the examples included herein.

Lipid esterases with reduced odor generation potential and good relative performance are particularly preferred as described in WO 2007/087243. These include(Novozyme)

Additional ingredients

The formulation may contain additional ingredients.

Additional surfactants

Surfactants are discussed in the Surfactant Science Series published by CRC Press, Series Editor, Arthur T.Hubbard.

The additional surfactant may be present at a preferred level of from 0.5 to 40 wt%, more preferably from 1 to 30 wt%.

The composition may preferably comprise a nonionic surfactant. Preferably, the nonionic surfactant is selected from saturated and monounsaturated fatty alcohol ethoxylates and saturated and monounsaturated fatty acid sugar esters. More preferably, the nonionic surfactant is a saturated and monounsaturated fatty alcohol ethoxylate, preferably selected from C having an average of 5 to 30 ethoxylates₁₂To C₂₀Linear primary alcohol ethoxylates, more preferably C having an average of 10 to 25 ethoxylates₁₆To C₁₈A linear primary alcohol ethoxylate.

The formulation may comprise an anionic detergent compound, which is preferably C₁₂To C₁₈Alkyl ether carboxylates and the water-soluble alkali metal salts of organic sulfuric, ether sulfuric, and sulfonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl groups.

Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially by reacting higher C' s₁₂To C₁₈Those obtained by sulfation of alcohols, alkyl radicals C₉To C₂₀Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C₁₀To C₁₅Sodium benzenesulfonate, alkyl (preferably methyl) ester sulfonates, and mixtures thereof.

Preferably these are present at a lower level than the glycerol carboxylate ester, preferably the weight fraction of additional anionic surfactant/glycerol carboxylate ester is from 0 to 0.4, preferably from 0 to 0.1.

Preferably, the surfactants used are saturated or monounsaturated. To prevent oxidation of the formulation, an antioxidant may be present in the formulation.

Builders or complexing agents

The composition may comprise a builder.

The builder material may be selected from 1) calcium sequestrant materials, 2) precipitation 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 well known representatives, such as zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and zeolites of the P-type as 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, carbonates being particularly preferred.

The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is generally present in a content of less than 15 wt.%, preferably less than 12.5 wt.%, more preferably less than 10 wt.%. Aluminosilicates are materials having the general formula:

0.8-1.5M₂O·Al₂O₃·0.8-6SiO_2,

wherein M is a monovalent cation, preferably sodium.

These materials contain some bound water and need to have a calcium ion exchange energy of at least 50mg CaO/gForce. Preferred sodium aluminosilicates contain 1.5-3.5 SiO in the above formula₂And (4) units. They can be easily prepared by reaction between sodium silicate and sodium aluminate, as well described in the literature. The ratio of surfactant to aluminosilicate (when present) is preferably greater than 5:2, more preferably greater than 3: 1.

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).

More preferably, the laundry detergent formulation is a non-phosphate-assisted laundry detergent formulation, i.e. containing less than 1 wt% phosphate. Most preferably, the laundry detergent formulation is unaided, i.e. contains less than 1 wt% of a builder.

If the detergent composition is an aqueous liquid laundry detergent, it is preferred that monopropylene glycol is present at a level of from 1 to 30 wt%, preferably from 2 to 18 wt%, to provide a suitable, pourable viscosity to the formulation.

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 fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt%, preferably from 0.005 to 2 wt%, more preferably from 0.01 to 0.1 wt%. Preferred classes of fluorescers are: distyrylbiphenyl compounds, such as Tinopal (trade mark) CBS-X, diaminostilbene disulfonic acid compounds, such as Tinopal DMS pure Xtra and Blankophor (trade mark) HRH, and pyrazoline compounds, such as Blankophor SN.

Preferred phosphors are those having CAS-No 3426-43-5, CAS-No 35632-99-6, CAS-No 2465-13-7, CAS-No 12224-16-7, CAS-No 13863-31-5, CAS-No4193-55-9, CAS-No 16090-02-1, CAS-No 133-66-4, CAS-No 68444-86-0, CAS-No 27344-41-8.

The most 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.

Perfume

The composition preferably comprises a perfume. Many suitable examples of fragrances are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide, published by CFTA Publications, and the OPD 1993Chemicals layers Directory 80th annular Edition, published by Schnell Publishing Co.

Preferably, the fragrance comprises at least one of the following notes (compounds): alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamic aldehyde; linalool; 2-methyl pentanoic acid ethyl ester; octanal; benzyl acetate; 3, 7-dimethyl-1, 6-octadien-3-ol 3-acetate; 2- (1, 1-dimethylethyl) -cyclohexanol 1-acetate; delta-damascone (damascone); beta-ionone; tricyclodecenyl acetate (verdyl acetate); laurinaldehyde; hexyl cinnamaldehyde (hexyl cinnnamic aldehyde); cyclopentadecanolide; 2-phenylethyl phenylacetate; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; α -irone; beta-phenylethyl benzoate; α -santalol; cedrol; cedryl acetate; cedryl formate (cedry format); cyclohexyl salicylate; gamma-dodecalactone, and beta-phenylethylphenyl acetate.

Useful components of perfumes include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components can be found in the literature, for example, in the Feraroli's Handbook of flavour Ingredients, 1975, CRC Press; synthetic Food adjacents, 1947, m.b. jacobs, edited by vannonstrand; or Perfun and flavour Chemicals, S.arctander, 1969, Montclair, N.J. (USA).

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

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 oil, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

The International Fragrance Association (The International Fragrance Association) has issued a list of Fragrance ingredients (fragrances) in 2011. (http:// www.ifraorg.org/en-us/ingredients #. U7Z4hPldWzk)

The perfumery Institute (The Research Institute for Fragrance Materials) provides a database of perfumes (fragrances) with safety information.

Perfume top notes can be used to suggest the whiteness and brightness benefits of the present invention.

Some or all of the perfume may be encapsulated, typical perfume components which facilitate encapsulation include those having a relatively low boiling point, preferably a boiling point of less than 300 ℃, preferably 100 ℃ and 250 ℃. It is also advantageous to encapsulate perfume components having a low Clog P (i.e. those that will have a higher tendency to be distributed into water), preferably having a Clog P of less than 3.0. These materials having relatively low boiling points and relatively low CLog P have been referred to as "delayed blooming" perfume ingredients and comprise one or more of the following materials: allyl hexanoate, amyl acetate, amyl propionate, anisaldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl isovalerate, benzyl propionate, β - γ hexenol, camphor gum, l-carvone, d-carvone, cinnamyl alcohol, cinnamyl formate (cinamyl form), cis-jasmone, cis-3-hexenyl acetate, cuminol, cyclal c, dimethyl benzyl methanol acetate, ethyl acetoacetate, ethyl ethylacetoacetate, ethylamyl ketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethylphenyl acetate, eucalyptol, eugenol, fenchyl acetate (fenchyl acetate), flor acetate (tricyclodecenyl acetate), tricyclodecene propionate, geraniol, hexenol, hexenyl acetate, hexyl acetate, Hexyl formate, solanol (hydroacetylalcohol), hydroxycitrocitronellal, indanone, isoamyl alcohol, isomenthone, isopulegyl acetate, isoquinolinone, ligustral, linalool oxide, linalyl formate, menthone, menthylacetone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benzyl acetate, methyl eugenol, methyl heptenone, methyl heptyne carbonate, methyl heptyne ketone, methyl hexyl ketone, methyl phenyl methyl acetate, methyl salicylate, methyl-N-methyl anthranilate, nerol, octolactone, octanol, p-cresol methyl ether, p-methoxyacetophenone, p-methylacetone, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, Phenylethyldimethylcarbinol, prenyl acetate, propyl borate, pulegone, rose oxide, safrole, 4-terpinenol (4-terpinenol), alpha-terpinenol and/or phenylacetaldehyde dimethanol acetal (viridine). It is common for multiple perfume components to be present in a formulation. In the compositions of the present invention, it is contemplated that there will be four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components present in the perfume from the given list of delayed release perfumes given above.

Another group of fragrances to which the present invention may be applied are the so-called "aromatherapy" materials. These include many components that are also used in perfumes, including components of essential oils such as sage, eucalyptus, geranium, lavender, Mace (Mace) extract, neroli, nutmeg, spearmint, sweet violet leaves and valerian.

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.

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

Enzymes such as proteases, amylases and cellulases may be present in the formulation.

The detergent composition optionally comprises one or more laundry adjunct ingredients.

The term "adjunct ingredient" includes: perfumes, dispersants, stabilizers, pH control agents, metal ion control agents, colorants, brighteners, dyes, odor control agents, pro-perfumes, cyclodextrins, perfumes, solvents, soil release polymers, preservatives, antimicrobials, chlorine scavengers, anti-shrinkage agents, fabric curling agents, stain removing agents, antioxidants, anti-corrosion agents, thickeners, drape and morphology control agents, smoothing agents, static control agents, wrinkle control agents, sanitizers, disinfectants, bacteria control agents, mold control agents, antiviral agents, antimicrobial agents, drying agents, stain resistance agents, soil release agents, odor control agents, fabric refreshers, chlorine bleach control agents, dye fixation agents, dye transfer inhibitors, hueing dyes, color maintenance agents, color restoration agents, revitalizing agents (rejuvenation agents), anti-fading agents, anti-wear enhancers, dyes, odor control agents, fabric refreshers, chlorine bleach control agents, dye fixation agents, dye transfer inhibitors, hueing dyes, color maintenance agents, color restoration, Anti-wear agents, fabric integrity agents, anti-wear and rinse aids, UV protection agents, sun fade inhibitors, insect repellents, anti-allergenic agents, enzymes, flame retardants, water repellents, fabric comfort agents, water conditioning agents, anti-wrinkle agents, anti-stretch agents, and combinations thereof. Such adjuvants, if present, may be present at a level of from 0.1% to 5% by weight of the composition.

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

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

Examples

To produce a detergent product containing 5 wt% surfactant in water at pH 7 with or without the addition of 0.01 wt% lipase (lipex)From Novozymes (EC 3.1.1.3)). COOP brand lard, purchased from COOP (uk), is stored in a domestic refrigerator and used as provided. A small portion of lard was placed in a glass test tube and melted by placing the lard in a batch of hot water. 0.070g of molten lard was placed in a small flat bottom glass tube (28ml tube) and allowed to solidify into a film on the bottom. The detergent product was added to water to give 10ml of a wash solution with pH 7, 20 ° FH, containing 0.5g/L surfactant and 0 or 1mg/L lipase. The detergent solution was added to the tube, the tube was sealed and placed in an incubator set at 40 ℃ with a shaker speed of 150rpm for 1 hour. After washing, the sample was placed in ice for 30 minutes, then the wash was removed and the tube was rinsed twice with 50ml of cold 24 ° FH water. Experiments were performed in triplicate. The samples were allowed to stand overnight (18 hours), and then the lard remaining in each tube was dissolved in 5ml of toluene and spotted using this solution onto a stainless steel MALDI plate. For each tube, 6 MALDI deposition spots were prepared, for a total of 18 measurements per condition. After evaporation of the toluene, MALDI mass spectra were measured on a Bruker Autoflex using 100% laser power.

The hydrolysis of lard by lipase was measured by the area of the relative areas of the peaks DG34:1 and DG35:0 of the diglycerides formed by hydrolysis of lard triglycerides.

DG x: y refers to a diglyceride having x carbon atoms (excluding glycerol groups) and a total of y carbon-carbon double bonds.

RA is the relative area of each glyceride peak and is calculated as follows

RA 100 x sum of diglyceride area/triglyceride area (TG48:1 to TG54:1)

The triglyceride peaks for the sum of triglyceride areas are TG48:1, TG50:3, TG50:2, TG50:1, TG50:0, TG51:1, TG51:0, TG52:4, TG52:3, TG52:2, TG52:1, TG52:0, TG53:2, TG53:1, TG53:0, TG54:6, TG54:4, TG54:3, TG54:2 and TG54: 1.

TGx y refers to a triglyceride having x carbon atoms (excluding glycerol groups) and a total of y carbon-carbon double bonds.

The 95% confidence limits were calculated from repeated experiments.

The results are shown in the following table.

DG34:1 results Table

Surface active agent	Control	95％	Lipase-containing enzyme	95％
					LES (2EO) COMPARATIVE EXAMPLE	2.7	0.5	15.1	0.8
SES (2EO) COMPARATIVE EXAMPLE	2.7	0.4	8.1	1.0
					C18Citrem invention	2.8	0.4	30.9	1.0
C18Datem invention	2.8	0.6	36.7	2.9

DG35:0 results Table

Surface active agent	Control	95％	Lipase-containing enzyme	95％
					LES (2EO) COMPARATIVE EXAMPLE	4.6	0.9	4.3	0.5
SES (2EO) COMPARATIVE EXAMPLE	2.7	0.5	4.3	1.2
					C18Citrem invention	3.1	0.4	5.8	1.0
C18Datem invention	3.2	0.8	7.0	1.1

LES (2EO) is a lauryl ether sulfate with 2 moles of ethoxylation.

SES (2EO) is stearyl ether sulfate with 2 moles of ethoxylation.

C18Datem is a diacetyl tartaric acid ester of monoglycerides prepared from edible, fully hydrogenated rapeseed oil.

C18Citrem is a citric acid ester of mono and diglycerides prepared from edible fully hydrogenated rapeseed oil.

Rapeseed oil contains more than 90% of C₁₈A fatty acid.

The relative concentration of diglycerides increases in the presence of lipase due to lipase hydrolysis of triglycerides. The lipase activity was strongest in the presence of C18Datem and C18Citrem, glycerol carboxylates, compared to the combination of lipase and conventional (non-ionic) surfactant.