Compositions comprising enzymes

Abstract

Disclosed is a composition comprising an anion-modified alkyl and / or alkenyl phenol polyoxyalkylene ether represented by formula (I) wherein R1 is a linear or branched alkyl or alkenyl group having 11 to 21 carbon atoms and an enzyme; each R2 is an alkylene oxide group having 2 to 4 carbon atoms; m is an integer from 1 to 50; e is a group comprising one or more of a sulfate radical, a phosphate radical, a carboxylate radical, a sulfonate radical, a sulfosuccinate radical, a sulfoacetate radical, a sarcosine radical and a phosphonate radical; m is a solubilizing cation selected from the group consisting of sodium, potassium, ammonium, monoalkanolamine, dialkanolamine, trialkanolamine, and mixtures thereof. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to compositions, particularly detergent compositions, comprising anionically modified alkyl and / or alkenylphenol polyoxyalkylene ethers and enzymes. Background Art

[0002] Enzymes are widely used in the detergent industry due to their function as efficient low temperature catalysts in the stain removal process. Commonly used enzymes are amylases (carbohydrate-containing stains), lipases (fat and edible oil stains), proteases (protein stains) and cellulases (removal of fuzz and lint from cotton fabrics). However, the stability of these enzymes in detergent compositions remains a major obstacle, particularly in liquid compositions. They are prone to reduced enzymatic activity during the shelf life of the detergent composition, resulting in reduced stain removal efficiency. Typically, the loss of activity results from many undesirable interactions between the enzyme and other components of the detergent composition.

[0003] Anionic surfactants are commonly used in detergent compositions due to their excellent cleaning ability to help remove oily and greasy substances. However, formulating anionic surfactants with enzymes is challenging because they strongly interact with enzymes by altering their tertiary structure, which leads to protein unfolding and loss of activity.

[0004] Today, bio-based compounds have gained significant attention due to the increased demand for sustainable alternatives to petroleum-based raw materials. Some consumers prefer compounds with good environmental properties. For the purpose of environmental sustainability, greener surfactant options may be used, especially those derived from raw materials of plant origin.

[0005] The present invention has been devised in light of the above considerations. It has been unexpectedly discovered that a composition comprising anionically modified alkyl and / or alkenylphenol polyoxyalkylene ethers and an enzyme provides improved enzyme stability and activity under storage conditions. Summary of the invention

[0006] In a first aspect, the present invention relates to a composition comprising:

[0007] a) Anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether represented by formula (I)

[0008]

[0009] wherein R1 is a straight or branched alkyl or alkenyl group having 11 to 21 carbon atoms; each R2 is an oxyalkylene group having 2 to 4 carbon atoms; m is an integer from 1 to 50; E is a group comprising one or more of sulfate, phosphate, carboxylate, sulfonate, sulfosuccinate, sulfoacetate, sarcosinate and phosphonate; M is a solubilizing cation selected from sodium, potassium, ammonium, monoalkanolamine, dialkanolamine, trialkanolamine and mixtures thereof; and

[0010] b) Enzymes.

[0011] In a second aspect, the present invention relates to a method for forming a liquid detergent composition or wash liquor by dispensing a dose of a composition according to any embodiment of the first aspect.

[0012]

[0013] All further aspects of the invention will become more readily apparent by consideration of the following detailed description and examples. DETAILED DESCRIPTION

[0013] Except in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or reaction conditions, physical properties of materials and / or use may optionally be understood as modified by the word "about".

[0014] Unless otherwise indicated, all amounts are by weight of the final composition.It should be noted that in specifying any range of values, any particular upper value can be associated with any particular lower value.

[0015] For the avoidance of doubt, 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.

[0016] The disclosure of the invention found herein is deemed to cover all embodiments present in claims that are multiply dependent on each other, regardless of the fact that the claims may exist without multiple dependency or redundancy.

[0017] Where a feature is disclosed with respect to a particular aspect of the invention (eg, a composition of the invention), such disclosure is also considered to apply mutatis mutandis to any other aspect of the invention (eg, a method of the invention).

[0018] Unless otherwise indicated, amounts used herein are expressed as weight percent based on the total weight of the composition and abbreviated as "wt %" or "weight %".

[0019] Unless otherwise stated, weight % enzyme amounts in compositions refer to weight % active protein levels.

[0020] The composition may have uses for various cleaning applications. Preferably, the composition is a detergent composition. The composition of the present invention may be in any suitable form, for example a solid, such as a powder, granular particles and shaped solids, or a liquid. Preferably, the composition is a liquid detergent composition. In the context of the present invention, the term "liquid" means that the continuous phase or major part of the composition is liquid and the composition is flowable at 15°C or above. Thus, the term "liquid" may include emulsions, suspensions and compositions with a flowable but harder consistency, referred to as gels or pastes. The viscosity of the composition may suitably be 25°C and 21sec. -1 The shear rate is in the range of about 200 to about 10,000 mPa·s. This shear rate is the shear rate normally applied to a liquid when pouring from a bottle. Pourable liquid detergent compositions typically have a viscosity of 200 to 1,500 mPa·s at 25°C and 21s -1 The shear rate was measured by HAAKE viscometer.

[0021] In some embodiments, the composition is a laundry detergent composition. In the context of the present invention, the term "laundry detergent" means a formulated composition intended for and capable of wetting and cleaning household clothing (such as clothes, linens and other household textiles). Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of an automatic washing machine, and liquid fine washing and liquid color care detergents, such as those detergents suitable for hand washing or washing delicate clothing (such as those made of silk or wool) in the wash cycle of an automatic washing machine. In some embodiments, the composition is a hand-washing detergent, which relates to consumers using their hands to wash substrates. Fields of use are primarily related to laundry purposes (i.e., hand-washing clothes) and hand-washing dishes (i.e., manual washing of dishes, etc.). Hand-washing detergents relate to the close contact of detergent liquid with hands during washing, whether in clothing washing or hand-washing dishes washing. Laundry detergent compositions are particularly preferred.

[0022] The composition may be concentrated or diluted. A "concentrated" composition refers to a composition comprising at most 50% by weight, such as at most 40%, at most 30% or at most 20% water, based on the total weight of the composition. Preferably, the composition of the present invention is a "dilute" composition. A "dilute" composition refers to a composition comprising more than 50% by weight, such as more than 60%, more than 70% or more than 80% water.

[0023] Anion-modified alkyl and / or alkenylphenol polyoxyalkylene ethers

[0024] The anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether is represented by formula (I):

[0025]

[0026] wherein R1 is a straight or branched alkyl or alkenyl group having 11 to 21 carbon atoms; each R2 is an oxyalkylene group having 2 to 4 carbon atoms; m is an integer from 1 to 50; E is a group comprising one or more of sulfate, phosphate, carboxylate, sulfonate, sulfosuccinate, sulfoacetate, sarcosinate and phosphonate; and M is a solubilizing cation selected from sodium, potassium, ammonium, monoalkanolamine, dialkanolamine, trialkanolamine and mixtures thereof.

[0027] Preferably, R1 is a linear or branched alkyl or alkenyl group having 13 to 17 carbon atoms, more preferably, R1 is a linear alkyl or alkenyl group having 13 to 17 carbon atoms. It is particularly preferred that R1 is a linear C15 alkyl or alkenyl group, more preferably a linear C15 alkyl or alkenyl group containing 0 to 3 carbon-carbon double bonds.

[0028] Preferably, each R2 is an ethylene oxide group or a propylene oxide group. More preferably, each R2 is an ethylene oxide group.

[0029] Preferably, m is an integer from 1 to 30, more preferably from 2 to 15 and most preferably from 3 to 10.

[0030] E is a terminal group comprising one or more of sulfate, phosphate, carboxylate, sulfonate, sulfosuccinate, sulfoacetate, sarcosinate and phosphonate, preferably E comprises sulfate, phosphate or a mixture thereof, more preferably E comprises or is sulfate. M is a solubilizing cation selected from sodium, potassium, ammonium, monoalkanolamine, dialkanolamine, trialkanolamine and a mixture thereof, preferably M is sodium, potassium or ammonium, more preferably M is sodium or ammonium.

[0031] It is understood that E is a terminal group carrying an anionic charge which is covalently bonded to the group R2. M is one or more cationic moieties which form ionic bonds with E to provide charge balance.

[0032] Preferably, the anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether is anion-modified alkyl and / or alkenylphenol polyoxyethylene ether, more preferably anion-modified cardanol polyoxyethylene ether.

[0033] Preferably, the anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether is an alkyl and / or alkenylphenol polyoxyalkylene ether sulfate, or an alkyl and / or alkenylphenol polyoxyalkylene ether phosphate, more preferably the anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether is an alkyl and / or alkenylphenol polyoxyethylene ether sulfate, or an alkyl and / or alkenylphenol polyoxyethylene ether phosphate.

[0034] It is particularly preferred that the anionically modified alkyl and / or alkenylphenol polyoxyalkylene ether is cardanol polyoxyalkylene ether sulfate or cardanol polyoxyalkylene ether phosphate, preferably cardanol polyoxyethylene ether sulfate or cardanol polyoxyethylene ether phosphate. Cardanol polyoxyethylene ether sulfate is most preferred.

[0035] Cardanol is a product obtained by processing cashew nut shell liquid (CNSL). CNSL is a well-known inedible natural oil obtained as a byproduct of cashew (Anacardium occidentale) fruit. CNSL is one of the most widely used bio-based resources for providing useful chemicals for various applications. Cardanol is an important chemical derived by decarboxylation of anacardic acid (which is the main component of CNSL). Cardanol is a natural biomass phenol with a C15 side chain (R) in the meta position of the aromatic ring, which is represented by formula (II). The side chain R is a straight-chain C15 alkyl or alkenyl group containing 0 to 3 carbon-carbon double bonds. Therefore, cardanol has four components, and each component has saturated, monoene, diene and triene structures, respectively. The position of the double bond is located at the 8th, 11th and 14th positions of the side chain R, respectively. The four components in cardanol are about 5-8% of a saturated component, about 48-49% of a component having one double bond, about 16-17% of a component having two double bonds, and about 29-30% of a component having three double bonds.

[0036]

[0037] The cardanol polyoxyethylene ether represented by the formula (III) can be formed through a polymerization-type reaction by reacting cardanol and ethylene oxide in the presence of a catalyst.

[0038]

[0039] wherein R is a straight chain C15 alkyl or alkenyl group containing 0 to 3 carbon-carbon double bonds as defined in formula (II) above. n is an integer from 1 to 50, preferably from 1 to 30, more preferably from 2 to 15, and most preferably from 3 to 10.

[0040] The reaction is generally referred to as ethoxylation. The reaction mechanism is: cardanol produces oxygen anions under alkaline conditions, and cardanol polyoxyethylene ether is obtained by ethoxylation reaction with ethylene oxide. Preferably, the molar ratio of cardanol to ethylene oxide is 1:100 to 20:1, more preferably 1:50 to 10:1, and even more preferably 1:30 to 1:1. Preferred catalysts for the reaction include, for example, potassium hydroxide, sodium hydroxide, barium hydroxide octahydrate, sodium bicarbonate or a mixture thereof. The amount of the catalyst is generally 0.01 to 5% by weight of cardanol, more preferably 0.1 to 3% by weight, even more preferably 0.2 to 1% by weight, and most preferably 0.4 to 0.6% by weight. The reaction temperature is preferably 120 to 180°C, and the polymerization reaction time is generally 0.5 to 2 hours. At the end of the polymerization reaction, the reaction product is generally neutralized with acetic acid to obtain cardanol polyoxyethylene ether. Other alkylene oxides, such as propylene oxide, can also be reacted with cardanol by polymerization to produce various cardanol polyoxyethylene ethers. Other examples of manufacturing methods suitable for producing the cardanol polyoxyethylene ethers described herein are disclosed in CN102432440A, CN102391080A, CN102351664A and CN101941894A.

[0041] Cardanol polyoxyethylene ether can be further functionalized with anionic groups to form anion-modified cardanol polyoxyethylene ether. Preferably, the anionic group is sulfate or phosphate, more preferably sulfate.

[0042] The cardanol polyoxyethylene ether sulfate represented by the formula (IV) can be formed by sulfonating cardanol polyoxyethylene ether in the presence of a catalyst.

[0043]

[0044] Wherein R is a straight chain C15 alkyl or alkenyl group containing 0 to 3 carbon-carbon double bonds as defined in formula (II) above. n is an integer from 1 to 50, preferably from 1 to 30, more preferably from 2 to 15, and most preferably from 3 to 10. M is a solubilizing cation selected from sodium, potassium, ammonium, monoalkanolamine, dialkanolamine, trialkanolamine and mixtures thereof, preferably M is sodium, potassium or ammonium, more preferably M is sodium or ammonium.

[0045] The preferred sulfonating agent is sulfamic acid or sodium sulfonate, more preferably sulfamic acid. The molar ratio of cardanol polyoxyethylene ether to the sulfonating agent is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, even more preferably 1:3 to 3:1, and most preferably 1:1.2 to 1:1.

[0046] Preferred catalysts for the reaction include, for example, carbonamide, dicyandiamide, urea, p-toluenesulfonic acid, dimethylformamide, N-methylpyrrolidone, hypophosphite or a mixture thereof, more preferably carbonamide, dicyandiamide, urea or a mixture thereof. The molar ratio of cardanol polyoxyethylene ether to the catalyst is preferably 1:10 to 30:1, more preferably 1:5 to 20:1, even more preferably 1:1 to 10:1, most preferably 1.5:1 to 5:1. It is preferred to include a reducing agent as a color stabilizer in the reaction mixture to obtain a light-colored cardanol polyoxyethylene ether sulfate. Preferably, the reducing agent includes hypophosphorous acid, hypophosphite or a mixture thereof.

[0047] The reaction temperature is preferably 100 to 125° C., and the reaction time is generally 3 to 6 hours. At the end of the reaction, an alcohol may be added to the reaction mixture to reduce the viscosity, thereby obtaining cardanol polyoxyethylene ether sulfate. The alcohol is preferably a C1-C4 monohydric alcohol, including methanol, ethanol, isobutanol or a mixture thereof. Alternatively, the reaction mixture may be neutralized with sodium hydroxide to obtain cardanol polyoxyethylene ether sulfate. Further examples of manufacturing methods suitable for producing the cardanol polyoxyethylene ether sulfate described herein are disclosed in CN114276281A and CN101941926A.

[0048] When aminosulfonic acid is used as the sulfonating agent, the counterion M of the resulting cardanol polyoxyethylene ether sulfate is ammonium. Examples are commercially available from Nasurfar Biomaterial Technology Co. Ltd. under the trade name NSN3003. The ammonium counterion can be replaced by sodium or potassium ions by ion exchange according to standard methods to produce sodium cardanol polyoxyethylene ether sulfate or potassium cardanol polyoxyethylene ether sulfate. Cardanol polyoxyethylene ether sulfates with sodium or potassium counterions are preferred because they can be more stable than the corresponding ammonium salts when formulated into the compositions of the present invention.

[0049] The composition of the present invention preferably comprises anionically modified alkyl and / or alkenylphenol polyoxyalkylene ether in an amount of 0.1 to 30%, more preferably 0.5 to 20%, even more preferably 1 to 15%, most preferably 2 to 10%, based on the total weight of the composition, and including all ranges subsumed therein.

[0050] Enzymes

[0051] The composition of the present invention comprises enzymes. Examples of enzymes suitable for use in the composition include proteases, lipases, amylases, mannanases, pectate lyases, cellulases, phospholipases, cutinases, peroxidases, oxidases or mixtures thereof. Proteases and amylases are most preferred.

[0052] Preferably, the composition comprises a protease. Proteases hydrolyze bonds within peptides and proteins, which, in the case of detergents, results in enhanced removal of stains containing proteins or peptides. Examples of suitable protease families include aspartic proteases; cysteine ​​proteases; glutamic proteases; asparagine peptide lysing enzymes; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk / ). Preferred are serine proteases. More preferred are subtilase-type serine proteases. The term "subtilase" refers to a subgroup of serine proteases according to Siezen et al., Protein Engng.4 (1991) 719-737 and Siezen et al., Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. Subtilases can be divided into six divisions, namely the Subtilisin family, Thermolysin family, Proteinase K family, Lantibiotic peptidase family, Kexin family and Pyrolysin family.

[0053] Examples of subtilases are those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, described in US7262042 and WO09 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168, described in WO89 / 06279, and protease PD138, described in (WO93 / 18140). Preferably, the subtilisin is derived from Bacillus, preferably Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, described in US 6,312,936 B1, US 5,679,630, US 4,760,025, US 7,262,042 and WO09 / 021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0054] Suitable commercially available proteases include those sold under the trade names Duralase TM 、Durazym TM , Ultra, Ultra, Ultra, Ultra, and Carnival TM Those sold, all of which are available as or (Novozymes A / S) for sale. Carnival TM It is particularly preferred.

[0055] Sold by Genencor International under the trade name Purafect Purafect and Purafect Those that are sold.

[0056] By product name Purafect PreferenzTM, Purafect Purafect Purafect EffectenzTm, and (Danisco / DuPont); Axapem TM Those sold by (Gist-Brocases NV).

[0057] Those available from Henkel / Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604, having the following mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP having S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP having S3T+V4I+V205I) and BLAP F49 (BLAP having S3T+V4I+A194P+V199M+V205I+L217D) - all from Henkel / Kemira; and KAP from Kao (alkalophilic Bacillus subtilisin having mutations A230V+S256G+S259N).

[0058] Preferably, the composition comprises an amylase. Amylases are enzymes that catalyze the hydrolysis of starch into sugars, which, in the case of detergents, results in enhanced removal of starch-containing stains. Suitable amylases (α and / or β) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Most preferred amylases include, for example, α-amylases obtained from Bacillus, such as a special strain of B. licheniformis described in more detail in GB 1,296,839, or a Bacillus strain disclosed in WO95 / 026397 or WO00 / 060060. Even more preferred (commercially available) amylases are available under the trade name Plus, Amplify and (from Novozymes A / S) and / Effect TM 、Powerase TM 、Preferenz S1000 TM 、Preferenz S110 TM and Preferenz S100 TM (from Genencor International Inc. / DuPont) for sale. Prime amylase is the most favorable of the commercial amylases.

[0059] The lipase may be any known lipase used in the field of detergent compositions. Preferred are lipases from Humicola (synonym Thermomyces), such as from other strains of H. lanuginosa (T. lanuginosus) or from H. insolens, Pseudomonas lipases, such as from P. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. stutzeri, P. fluorescens, Pseudomonas strain SD 705 (WO 95 / 06720 and WO 96 / 27002), Pseudomonas wisconsinensis, Bacillus lipases, for example, from Bacillus subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), Bacillus stearothermophilus (JP 64 / 744992) or Bacillus pumilus (WO 91 / 16422). Even more preferred (commercially available) lipases are available under the trade name Lipolase and (from Novozymes A / S), and bacterial enzymes from Genecor This is a lipase of bacterial origin, such as variant M21L of the Pseudomonas alcaligenes lipase described in WO 94 / 25578 to Gist-Brocades (MMMJ Cox, HBM Lenting, LJSMM Mulleners and JM van der Laan). Lipase is most preferred.

[0060] Suitable mannanases include those of bacterial and fungal origin. More preferred are mannanases derived from the filamentous fungus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (WO 94 / 25576); Trichoderma reseei (as disclosed in WO 93 / 24622); Bacillus organisms (e.g., as described in Talbot et al., Appl. Environ. Microbiol. Vol. 56, No. 11, pp. 3505-3510 (1990), which describes mannanases derived from Bacillus stearothermophilus, Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994), which describes a β-mannanase from Bacillus subtilis, JP-A-03047076, which describes a β-mannanase from Bacillus, JP-A-63056289, which describes the production of an alkaline, thermostable β-mannanase; JP-A-63036775, which describes a Bacillus microorganism FERMP-8856 that produces β-mannanase and β-mannosidase, JP-A-08051975, which describes an alkaline β-mannanase from alkalophilic Bacillus AM-001, WO 97 / 11164, which describes a purified mannanase from Bacillus amyloliquefaciens, WO 91 / 18974 which describes hemicellulases such as glucanase, xylanase or mannanase activity). Also preferred are alkaline family 5 and 26 mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus and Humicola insolens (as disclosed in WO 99 / 64619). More preferred bacterial mannanases are those described in WO 99 / 64619. Even more preferred (commercially available) mannanases are available from Novozymes A / S Denmark.

[0061] Pectate lyase is also called polygalacturonate lyase. Preferred are pectate lyases derived from bacterial genera such as Erwinia, Pseudomonas, Klebsiella and Xanthomonas, Bacillus. More preferred are those from Bacillus subtilis (Nasser et al. (1993) FEBS Lett. 335: 319-326), Bacillus YA-14 (Kim et al. (1994) Biosci. Biotech. Biochem. 58: 947-949); Bacillus pumilus (Dave and Vaughn (1971) J. Bacteriol. 108: 166-174), Bacillus polymyxa (Nagel and Vaughn (1961) Arch. Biochem. Biophys. 93: 344-352), Bacillus stearothermophilus (Karbassi and Vaughn (1980) Can. J. Microbiol. 26: 377-384), Bacillus (Hasegawa and Nagel (1966) J. Food Sci. 31: 838-845), Bacillus RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24: 1164-1172), as disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331-334, Henrissat et al. (1995) Plant Physiol. 107: 963-976, as disclosed in WO 99 / 27083, WO 99 / 27084, US 6,284,524 (which documents are incorporated herein by reference), WO 02 / 006442 (particularly as disclosed in the Examples, which documents are incorporated herein by reference). Even more preferred (commercially available) pectate lyases are those from Novozymes A / S, Denmark. L and Pectate lyase is most preferred.

[0062] Suitable cellulases include those of bacterial, fungal, insect and / or mammalian origin. Chemically modified or protein engineered mutants are included. More preferably, cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, such as fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporu disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, WO 96 / 029397 and WO 98 / 012307. Even more preferred (commercially available) cellulases are Endolase TM , (Novozymes A / S), Clazinase TM and Puradax HA TM (Genencor International Inc.) and KAC-500(B) TM (Kao Corporation). Cellulases are most preferred.

[0063] Phospholipases are classified as EC 3.1.1.4 and / or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme active on phospholipids. Phospholipids, such as phosphatidylcholine or phosphatidylcholine, consist of glycerol esterified with two fatty acids at the outer (sn-1) and middle (sn-2) positions and esterified with phosphoric acid at the third position; the phosphoric acid can be esterified to an amino alcohol. Phospholipases are enzymes involved in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phosphatase A1 and A2, which hydrolyze one fatty acyl group (located at the sn-1 and sn-2 positions, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze the remaining fatty acyl groups in lysophospholipids. Phospholipase C and phospholipase D (phosphodiesterase) release diacylglycerol or phosphatidic acid, respectively.

[0064] Cutinases are classified in EC 3.1.1.74. The Cutinase used according to the present invention may be of any origin. Preferably the Cutinase is of microbial origin, more preferably of bacterial, fungal or yeast origin.

[0065] Suitable peroxidases / oxidases are of bacterial, fungal or mammalian origin, and more preferably of bacterial origin. Chemically modified or protein engineered mutants are included. Preferably, the peroxidase / oxidase is derived from Aeromonas sp.

[0066] The compositions of the present invention preferably comprise from 0.00001 to 1 wt %, more preferably from 0.0001 to 0.5 wt %, even more preferably from 0.0005 to 0.4 wt %, still even more preferably from 0.001 to 0.3 wt %, and most preferably from 0.001 to 0.2 wt % enzyme based on the total weight of the composition, and including all ranges subsumed therein. The amount of wt % enzyme in the composition refers to the wt % of the active protein level.

[0067] The enzyme may be added to the composition in liquid, granular or encapsulated form, but is preferably unencapsulated. The composition may also contain an enzyme stabilizer, such as a polyol (such as propylene glycol or glycerol), a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative (such as an aromatic borate) or a phenylboronic acid derivative (such as 4-formylphenylboronic acid), and the composition may be formulated as described in, for example, WO 92 / 19709 and WO 92 / 19708.

[0068] Surfactants

[0069] In addition to the anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether, the composition may also include other surfactants. Suitable surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants or mixtures thereof, preferably surfactants include anionic surfactants, nonionic surfactants or mixtures thereof.

[0070] Anionic surfactants that can be used for preferred types of the present invention include alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologous alkyl chain homologues, each containing an aromatic ring that is sulfonated in the "para-position" and is connected to a linear alkyl chain at any position except the terminal carbon. The linear alkyl chain usually has a chain length of 11 to 15 carbon atoms, wherein the main material has a chain length of about C12. Every kind of alkyl chain homologue is composed of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is usually formulated into the composition in the form of acid (i.e. HLAS), and then at least partially in situ neutralization. The example of alkylbenzene sulfonate includes sodium salt, alkyltoluene sulfonate, alkylxylene sulfonate, alkylphenol sulfonate, alkylnaphthalene sulfonate, diamylnaphthalene sulfonate and dinonylnaphthalene sodium sulfonate of linear alkylbenzene sulfonic acid, and a mixture with olefin sulfonate.

[0071] Some alkyl sulfate surfactants (PAS), such as non-ethoxylated primary and secondary alkyl sulfates having an alkyl chain length of 10 to 18, may be used.

[0072] Another anionic surfactant commonly used in the composition is an alkyl ether sulfate having a straight or branched alkyl group of 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which the main C 12 The lauryl alkyl groups are ethoxylated with an average of 2 EO units per molecule.

[0073] Alkyl ether sulfates may be present in the composition. Preferably, the composition is substantially free of alkyl ether sulfates. As used herein, "substantially free" means less than 1.5 weight percent, preferably less than 1.0 weight percent, more preferably less than 0.75 weight percent, still more preferably less than 0.5 weight percent, even more preferably less than 0.1 weight percent, most preferably 0 to 0.01 weight percent, including all ranges subsumed therein, based on the total weight of the composition. It is preferred that the composition does not contain any alkyl ether sulfates.

[0074] When the composition contains other anionic surfactants in addition to the anionically modified alkyl and / or alkenylphenol polyoxyalkylene ether, the total amount of anionic surfactants in the composition is preferably in the range of 0.1 to 60%, more preferably 1 to 55%, even more preferably 3 to 50% based on the total weight of the composition, and including all ranges subsumed therein.

[0075] The composition can also include nonionic surfactants. Nonionic surfactants used in the present invention include, for example, a) polyoxyalkylene compounds, i.e., the reaction product of an alkylene oxide (such as ethylene oxide or propylene oxide or a mixture thereof) and a starting molecule having a hydrophobic group and a reactive hydrogen atom that reacts with the alkylene oxide. Such starting molecules include alcohols, acids, amides or alkylphenols. In the case where the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. Polyoxyalkylene compounds can have a variety of block and mixed (random) structures. For example, they can include a single block of alkylene oxide, or they can be a diblock alkoxylate or a triblock alkoxylate. In the block structure, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a mixed mixture of alkylene oxides. Examples of such materials include C8 to C 22 Alkylphenol ethoxylates having an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol; and alkyl alcohol ethoxylates, such as C8 to C 18 a) a primary or secondary straight or branched chain alcohol ethoxylate having an average of 2 to 40 moles of ethylene oxide per mole of alcohol; b) a fatty acid amide; c) an alkoxylated glyceride; d) an alkyl polyglycoside; e) a rhamnolipid; or mixtures thereof.

[0076] A preferred class of nonionic surfactants for use in the present invention includes C8 to C 18 Alkyl alcohol ethoxylate, more preferably C 12 To C 15 Primary straight chain alcohol ethoxylates having an average of 3 to 20, more preferably 3 to 10, moles of ethylene oxide per mole of alcohol. Particularly preferred are lauryl alcohol condensed with 3, 5, 7 and 9 moles of EO (AEO-3, AEO-5, AEO-7 and AEO-9).

[0077] Another preferred type of nonionic surfactant for the present invention includes fatty acid amides. Preferably, fatty acid amides contain at least 6 carbon atoms. Suitable fatty acids preferably contain 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms, most preferably 12 to 18 carbon atoms. In the most preferred embodiment of the present invention, amides of essential fatty acids are used. Amides suitable for the present invention can be simple amides (i.e., those containing -CONH2), N-alkylamides, N,N-dialkylamides, mono-alkanolamides and di-alkanolamides. Suitable alkyl or alkanol groups contain 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, most preferably 1 to 8 carbon atoms. Preferred amides included in the present invention are mono-alkanolamides and di-alkanolamides, particularly amides of essential fatty acids. Alkanolamides are generally more available than alkylamides.

[0078] Preferably, the fatty acid amide is a fatty alkanolamide (fatty acid alkanolamide), more preferably C8 to C 20 Fatty acid C1 to C8 alkanolamides. Preferred fatty acid amides are selected from the monoethanolamide and diethanolamide of linoleic acid, palmitic acid and coconut oil. More preferably, the fatty acid amides include cocamide MEA, cocamide DEA, lauramide DEA, palm kernelamide DEA, stearamide MEA, myristicamide DEA, stearamide DEA, oleamide DEA, tallowamide DEA, tallowamide MEA, isostearamide DEA, isostearamide MEA, cocamide MIPA or mixtures thereof. Palm kernelamide DEA is particularly preferred.

[0079] Another preferred class of nonionic surfactants are alkoxylated glycerides. Alkoxylated glycerides are represented by formula (V):

[0080]

[0081] wherein each of R1 to R6 is independently hydrogen or methyl; each of R7 to R9 is independently a linear or branched alkyl or alkenyl group having 5 to 30 carbon atoms, preferably 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms; m, n, p, x, y or z is independently a number from 1 to 30, preferably 5 to 25 and more preferably 12 to 21. The sum of m, n, p, x, y, z is in the range of 3 to 90.

[0082] Preferably, the alkoxylated glyceride comprises coconut fatty acid esters. Coconut or coconut oil fatty acids include about 82% by weight saturated fatty acids, and of the total fatty acid content, lauric acid is the most common, accounting for about 48% by weight of the fatty acid content. Myristic acid (16% by weight) and palmitic acid (9.5% by weight) are the next most common. Oleic acid is the most common unsaturated acid present at about 6.5% by weight of the fatty acid content.

[0083] Preferably, the alkoxylated glyceride comprises palm oil fatty acid ester. Palm oil has a balanced fatty acid composition, in which the level of saturated fatty acids is almost equal to the level of unsaturated fatty acids. Palmitic acid (44%-45%) and oleic acid (39%-40%) are the main component acids, as well as linoleic acid (10%-11%) and only trace amounts of linolenic acid. Compared with palm oil, palm kernel oil contains more saturated fatty acids. The main fatty acids in palm kernel oil are about 48% lauric acid, 16% myristic acid and 15% oleic acid. The most preferred alkoxylated glyceride is palm kernel oil ethoxylate. Examples can be commercially available from Sinolight Surfactant Technology Co., Ltd under the trade name SOE-N-60.

[0084] Other suitable alkoxylated glycerides are commercially available from Kao under the trade name Levenol. variants, such as Levenol F-200 having an average EO of 6 and a molar ratio of glycerol to coconut fatty acids of 0.55, Levenol V501 / 2 having an average EO of 17 and a molar ratio of glycerol to coconut fatty acids of 1.5, and Levenol C201 also known as Glycereth-17 Cocoate.

[0085] Another class of nonionic surfactants that can be used according to the present invention are glycoside surfactants. Alkyl polyglycoside surfactants suitable for use according to the present invention include those of the following formula:

[0086] RO-(R 2 O) y -(Z) x

[0087] wherein R is a monovalent organic group containing from about 6 to about 30 (preferably from about 8 to about 18) carbon atoms; 2is a divalent hydrocarbon radical containing about 2 to 4 carbon atoms; O is an oxygen atom; y is a number which can have an average value of 0 to about 12, but is most preferably 0; Z is a moiety derived from a reducing sugar containing 5 or 6 carbon atoms; and x is a number which has an average value of 1 to about 10 (preferably about 1 1 / 2 to about 10).

[0088] A particularly preferred group of glycoside surfactants for use in practicing the present invention include those having the above formula wherein R is a monovalent organic group (straight or branched) containing from about 6 to about 18 (especially from about 8 to about 18) carbon atoms; y is 0; z is glucose or a moiety derived therefrom; and x is a number having an average value of 1 to about 4 (preferably from about 1 1 / 2 to 4).

[0089] Preferably, the nonionic surfactant comprises an alkyl alcohol ethoxylate. A mixture of two or more nonionic surfactants may be used. When the composition comprises a nonionic surfactant, the nonionic surfactant is typically present at a level of 0.01 to 30%, more preferably 0.1 to 20%, and most preferably 1 to 10%, based on the total weight of the composition, and including all ranges contained therein.

[0090] The composition may also include one or more types of cationic surfactants. Many cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms may be present as an auxiliary component of the surfactant system. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, which is incorporated herein by reference.

[0091] Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof (in which one or two hydroxyethyl groups replace one or two methyl groups), and mixtures thereof. More cationic surfactants that can be used as surfactants are described in detail in U.S. Patent No. 4,497,718, which is incorporated herein by reference. Like nonionic and anionic surfactants, the compositions of the present invention can use cationic surfactants alone or in combination with any other surfactants known in the art. When a cationic surfactant is included, the cationic surfactant can be present in an amount in the range of 0 to 5%, based on the gross weight of the composition. It is preferred that the composition does not contain any cationic surfactant.

[0092] The composition may also include one or more types of amphoteric surfactants. Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycolates, alkyl amidopropyl hydroxysulfobetaines, acyltaurates and acylglutamates, which have an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of the higher acyl group. When amphoteric (zwitterionic) surfactants are included, the amphoteric (zwitterionic) surfactant may be present in an amount ranging from 0 to 5%, based on the total weight of the composition. It is preferred that the composition does not include any amphoteric surfactants.

[0093] Detergent

[0094] Builders enhance or maintain the cleaning efficiency of surfactants primarily by reducing water hardness. This is accomplished by sequestration or chelation (thereby keeping hardness minerals in solution), by precipitation (thereby forming insoluble materials), or by ion exchange (thereby exchanging charged particles). Suitable builders may be of organic or inorganic type, or mixtures thereof.

[0095] Suitable inorganic builders include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites and mixtures thereof. Specific examples of such materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

[0096] Suitable organic builders include polycarboxylic acids in acid and / or salt form. When used in salt form, alkali metals (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of this class of materials include sodium citrate and potassium citrate, sodium tartrate and potassium tartrate, sodium and potassium salts of tartrate monosuccinic acid, sodium and potassium salts of tartrate disuccinic acid, sodium ethylenediaminetetraacetate and potassium ethylenediaminetetraacetate, N-(2-hydroxyethyl)-ethylenediaminetriacetic acid sodium and N-(2-hydroxyethyl)-ethylenediaminetriacetic acid sodium potassium, sodium nitrilotriacetate and potassium nitrilotriacetate, and sodium N-(2-hydroxyethyl)-nitrilodiacetate and potassium N-(2-hydroxyethyl)-nitrilodiacetate. Polymeric polycarboxylic acids may also be used, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, vinyl acetic acid and crotonic acid) and / or unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, mesaconic acid and citraconic acid and anhydrides thereof). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in the form of an acid, a salt, or partially neutralized, and may suitably have a molecular weight (Mw) ranging from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, more preferably from about 2,500 to about 75,000.

[0097] It is particularly preferred that the builder is a phosphate chelating agent. Examples of phosphate chelating agents suitable for use in the composition include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP), aminotri(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), tetramethylenediaminetetra(methylenephosphonic acid) (TDTMP), phosphonobutanetricarboxylic acid (PBTC) or mixtures thereof, preferably 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) or mixtures thereof. Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) is particularly preferred.

[0098] The chelating agent may be in the form of an acid or a corresponding salt. Preferably, the chelating agent is in the form of a corresponding salt, more preferably an alkali metal salt, and even more preferably a sodium salt.

[0099] Mixtures of any of the above materials may also be used.

[0100] The compositions of the present invention preferably comprise detergent builders in an amount of 0.01 to 10%, more preferably 0.1 to 5%, even more preferably 0.25 to 4%, most preferably 0.5 to 2.5%, based on the total weight of the composition, and including all ranges subsumed therein.

[0101] Hydrotrope

[0102] The compositions of the present invention preferably include a non-aqueous carrier, such as a hydrotrope, a co-solvent, and a phase stabilizer. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids, such as C1 to C5 monohydric alcohols (such as ethanol and n-propanol or isopropanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); having a weight average molecular weight (M) ranging from about 200 to 600. w ) polyethylene glycol; C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as sodium and potassium xylene, toluene, ethylbenzene and isopropylbenzene (cumene) sulfonates).

[0103] Mixtures of any of the above materials may also be used.

[0104] When included, the non-aqueous carrier can be present in an amount of 0.01 to 50 wt %, preferably 0.05 to 30 wt %, more preferably 0.1 to 15 wt %, and even more preferably 0.2 to 5 wt % of the composition, based on the total weight of the composition, and including all ranges contained therein. The amount of hydrotrope used is associated with the amount of surfactant, and it is desirable to use the hydrotrope content to control the viscosity in such compositions. Preferred hydrotropes are monopropylene glycol, glycerol, triethanolamine, or mixtures thereof.

[0105] Soil Release Polymers

[0106] Soil release polymers (SRPs) help improve the release of soils from fabrics by modifying the fabric surface during washing. The adsorption of SRPs on the fabric surface is promoted by the affinity between the chemical structure of the SRP and the target fibers.

[0107] The compositions of the present invention preferably include SRP. The SRP used in the present invention may include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups to control molecular weight or change polymer properties, such as surface activity. The weight average molecular weight (M) of the SRP is preferably 100%. w ) may suitably be in the range of about 1000 to about 20,000, and preferably in the range of about 1500 to about 10,000.

[0108] The SRP used in the present invention can be suitably selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly(ethylene glycol) ("PEG"); partially and fully anionically terminated oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and sodium 3,6-dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block polyester oligomeric compounds, such as those prepared from a combination of DMT, Me terminated PEG, and EG and / or PG, or DMT, EG and / or PG, Me terminated PEG, and sodium dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0109] Other types of SRPs useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses; polymers having poly(vinyl ester) hydrophobic segments, such as graft copolymers of poly(vinyl esters), for example, C1-C6 vinyl esters such as poly(vinyl acetate) grafted onto a polyalkylene oxide backbone; poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam and polyethylene glycol.

[0110] Preferred SRPs for use in the present invention include copolyesters formed by condensation of terephthalate and a diol (preferably 1,2 propylene glycol) and further comprising endcaps formed by alkyl-terminated alkylene oxide repeating units. Examples of such materials have structures corresponding to formula (VI):

[0111]

[0112] Where R 14 and R 15 Independently of each other, X-(OC2H4) q -(OC3H6) s ;

[0113] Where X is C 1-4 Alkyl, and preferably methyl;

[0114] q is a number from 12 to 120, preferably from 40 to 50;

[0115] s is a number from 1 to 10, preferably from 1 to 7; and

[0116] i is a number from 4 to 9.

[0117] Because they are average values, q, s, and i are not necessarily integers for large batches of polymers.

[0118] Mixtures of any of the above materials may also be used.

[0119] When SRP is included, the overall content of SRP can range from 0.1 to 10 weight percent of the composition, depending on the level of polymer intended for use in the final composition, and desirably from 0.3 to 7 weight percent, more preferably from 0.5 to 5 weight percent, based on the total weight of the composition, and including all ranges subsumed therein.

[0120] Suitable SRPs are described in more detail in U.S. Pat. Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850, and WO 2016 / 005271. If used, SRPs are typically incorporated into the compositions herein at a concentration of 0.01 to 10 wt %, more preferably 0.1 to 5 wt %, based on the weight of the composition.

[0121] Polymeric cleaning enhancers

[0122] To further improve the environmental profile of the composition, it may be preferred in some cases to reduce the volume of the composition added per wash load and to add various weight efficient ingredients to the composition to enhance cleaning performance. In addition to the soil release polymers of the present invention described above, the compositions of the present invention also preferably contain one or more additional polymeric cleaning enhancers, such as anti-redeposition polymers.

[0123] Anti-redeposition polymers stabilize soil in the wash solution, thereby preventing redeposition of soil. Suitable anti-redeposition polymers for use in the present invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethyleneimine units -CH2CH2NH-, and when branched, the hydrogen on the nitrogen is replaced by another chain of ethyleneimine units. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (MW) of about 300 to about 10,000. w ). The polyethyleneimine backbone can be linear or branched. It can be branched to the extent that it is a dendritic polymer. The alkoxylation can generally be ethoxylation or propoxylation, or a mixture of the two. When the nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10 to 30, preferably 15 to 25 alkoxy groups per modification. The preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation per ethoxylated nitrogen atom in the polyethyleneimine backbone is 10 to 30, preferably 15 to 25 ethoxy groups.

[0124] Mixtures of any of the above materials may also be used.

[0125] When included, the compositions of the present invention preferably comprise from 0.025 to 8% by weight of one or more anti-redeposition polymers, such as, for example, an alkoxylated polyethyleneimine as described above.

[0126] preservative

[0127] The composition preferably comprises a preservative or a mixture of preservatives. Preferably, the preservative is selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and their salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, most preferably sodium benzoate. The preservative is preferably present in an amount of 0.01 to 3%, preferably 0.3% to 1.5% by weight of the composition. The weight is calculated for the protonated form.

[0128] Fluorescent agent

[0129] It may be advantageous to include a fluorescent agent (fluorescent whitening agent) in the composition. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts (e.g., sodium salts). The total amount of one or more fluorescent agents used in the composition is generally 0.005 to 2%, more preferably 0.01 to 0.5%, by weight of the composition.

[0130] Preferred types of fluorescent agents are: distyrylbiphenyl compounds such as Tinopal (trademark) CBS-X; diaminestilbene disulfonic acid compounds such as Tinopal DMS Pure Xtra, Tinopal 5BMGX and Blankophor (trademark) HRH, and pyrazoline compounds such as Blankophor SN.

[0131] Preferred fluorescent agents are: sodium 2-(4-phenylvinyl-3-sulfophenyl)-2H-naphtho[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-phenylvinyl-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'disulfonate and disodium 4,4'-bis(2-sulfostyryl)biphenyl. Most preferably, the fluorescent agent is a distilbene biphenyl compound, preferably sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethylene-2,1-diyl))dibenzenesulfonate (CAS-No 27344-41-8).

[0132] Defoaming agent

[0133] The composition may also include an anti-foaming agent. Anti-foaming materials are well known in the art and include silicones, fatty acids, fatty alcohols and EO-PO block copolymers.

[0134] Preferably, when present, the fatty acid antifoam agent is present at from 1.3 to 3.0%, more preferably from 1.4 to 2.0%, most preferably from 1.6 to 1.65% by weight of the composition.

[0135] In the context of the present invention, suitable fatty acids include those of the formula R 12 aliphatic carboxylic acid of COOH, where R 12 It is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms and 0 or 1 double bond.

[0136] Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures, wherein 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can generally be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0137] The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts of organic bases such as monoethanolamine, diethanolamine or triethanolamine. In the context of the present invention, suitable fatty alcohols include those of the formula R 13 OH aliphatic alcohol, where R 13 It is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms.

[0138] In the context of the present invention, suitable EO-PO block copolymers include polymers having repeating units of ethylene oxide and propylene oxide and having a hydrophilic-lipophilic balance (HLB) value of 4 or less.

[0139] Mixtures of any of the above materials may also be used.

[0140] For formulation calculation purposes, fatty acids and / or salts thereof (as defined above) are not included in the level of surfactant or in the level of builder in the formulation.

[0141] Color dye

[0142] Shading dyes can be used to improve the properties of the composition. Preferred dyes are violet or blue. It is believed that low levels of these shades of dye deposited on fabrics mask the yellowing of the fabric. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.

[0143] Hueing dyes are well known in the art of laundry liquid formulations.

[0144] Suitable and preferred classes of dyes are described below.

[0145] Direct dyes:

[0146] Direct dyes (also called substantive dyes) are the class of water-soluble dyes that have an affinity for fibers and are directly absorbed. Direct violet and direct blue dyes are preferred.

[0147] Preferably, disazo or trisazo dyes are used.

[0148] Most preferably, the direct dye is direct violet of the following structure:

[0149]

[0150]

[0151] in:

[0152] Rings D and E may independently be naphthyl or phenyl as shown;

[0153] R1 is selected from: hydrogen and C1-C4 alkyl, preferably hydrogen;

[0154] R2 is selected from the group consisting of: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

[0155] R3 and R4 are independently selected from: hydrogen and C1-C4 alkyl, preferably hydrogen or methyl;

[0156] X and Y are independently selected from: hydrogen, C1-C4 alkyl and C1-C4 alkoxy; preferably, the dye has X=methyl; and Y=methoxy and n is 0, 1 or 2, preferably 1 or 2.

[0157] Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51 and direct violet 99. Disazo copper containing dyes may be used, for example direct violet 66. Less preferred are benzidine based dyes.

[0158] Preferably, the direct dye is present in an amount of from 0.000001 to 1%, more preferably from 0.00001 to 0.0010% by weight of the composition.

[0159] In another embodiment, the direct dye may be covalently linked to a photobleach, for example as described in WO2006 / 024612.

[0160] Acid dyes:

[0161] Cotton-affinity acid dyes impart benefits to cotton-containing garments. Preferred dyes and dye mixtures are blue or violet. Preferred acid dyes are:

[0162] (i) Azine dyes, wherein the dye has the following core structure:

[0163]

[0164] Where R a , R b , R c and R d is selected from: H, branched or linear C1 to C7 alkyl chains, benzyl, phenyl and naphthyl;

[0165] The dye is at least one SO3 - or -COO - group substitution;

[0166] Ring B does not carry a negatively charged group or a salt thereof; and

[0167] Ring A may be further substituted to form a naphthyl group; the dye is optionally substituted with a group selected from amine, methyl, ethyl, hydroxy, methoxy, ethoxy, phenoxy, Cl, Br, I, F and NO2.

[0168] Preferred azine dyes are: Acid Blue 98, Acid Violet 50 and Acid Blue 59, with Acid Violet 50 and Acid Blue 98 being more preferred.

[0169] Other preferred non-azine acid dyes are Acid Violet 17, Acid Black 1 and Acid Blue 29.

[0170] Preferably, the acid dye is present at from 0.0005% to 0.01% by weight of the composition.

[0171] Hydrophobic dyes:

[0172] Composition can comprise one or more hydrophobic dyes selected from benzodifuran, methine, triphenylmethane, naphthalimide, pyrazole, naphthoquinone, anthraquinone and monoazo or disazo dye chromophore.Hydrophobic dye is the dyestuff that does not contain any charged water solubilizing group.Hydrophobic dye can be selected from disperse dye and solvent dye.Blue and violet anthraquinone and monoazo dye are preferred.

[0173] Preferred dyes include Solvent Violet 13, Disperse Violet 27, Disperse Violet 26, Disperse Violet 28, Disperse Violet 63 and Disperse Violet 77.

[0174] Preferably, the hydrophobic dye is present at from 0.0001% to 0.005% by weight of the composition.

[0175] Basic dyes:

[0176] Basic dyes are organic dyes with a net positive charge. They deposit on cotton. They have particular use in compositions containing primarily cationic surfactants. The dye may be selected from the basic violet and basic blue dyes listed in the Colour Index International.

[0177] Preferred examples include triarylmethane basic dyes, methane basic dyes, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.

[0178] Reactive dyes:

[0179] Reactive dyes are dyes that contain organic groups that react with cellulose and link the dye to cellulose through covalent bonds. They deposit on cotton.

[0180] Preferably, the reactive groups are hydrolysed or the reactive groups of the dye are reacted with an organic substance (eg a polymer) to attach the dye to that substance.The dye may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.

[0181] Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.

[0182] Dye conjugates:

[0183] Dye conjugates are formed by combining direct dyes, acid dyes or basic dyes with polymers or particles via physical forces. Depending on the choice of polymer or particle, they are deposited on cotton or synthetic fibers. Descriptions are given in WO2006 / 055787.

[0184] Particularly preferred dyes are: Direct Violet 7, Direct Violet 9, Direct Violet 11, Direct Violet 26, Direct Violet 31, Direct Violet 35, Direct Violet 40, Direct Violet 41, Direct Violet 51, Direct Violet 99, Acid Blue 98, Acid Violet 50, Acid Blue 59, Acid Violet 17, Acid Black 1, Acid Blue 29, Solvent Violet 13, Disperse Violet 27, Disperse Violet 26, Disperse Violet 28, Disperse Violet 63, Disperse Violet 77 and mixtures thereof.

[0185] The hueing dye may be used in the absence of a fluorescent agent, but it is particularly preferred to use a hueing dye in combination with a fluorescent agent, for example in order to reduce yellowing due to chemical changes in the adsorbed fluorescent agent.

[0186] External structurants

[0187] The compositions of the present invention can further modify their rheology by using one or more external structurants that form a structured network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose, and citrus pulp fibers. The presence of an external structurant can provide shear thinning rheology and can also enable materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0188] Fragrance

[0189] Fragrances are well known in the art and may be incorporated into the compositions described herein. Preferably, the fragrance is provided as a fragrance oil, and more preferably, the fragrance oil acts as a carrier for the additional antioxidant when used.

[0190] Preferably, the fragrance comprises phenols and / or ketones.

[0191] Microcapsules

[0192] One type of microparticle suitable for use in the present invention is a microcapsule.

[0193] Microencapsulation can be defined as the process of surrounding or encapsulating one substance within another on a very small scale, thereby producing capsules ranging in size from less than 1 micron to several hundred microns. The encapsulated material can be referred to as the core, active ingredient or agent, filler, payload, core, or internal phase. The material encapsulating the core can be referred to as a coating, membrane, shell, or wall material.

[0194] Microcapsules typically have at least one generally spherical continuous shell surrounding a core. The shell may contain pores, vacancies or interstitial openings, depending on the materials and encapsulation techniques employed. Multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of varying thickness around the core. Alternatively, the microcapsules may be asymmetrically and variably shaped, with a certain amount of smaller droplets of core material embedded throughout the microcapsule.

[0195] The shell may have a barrier function to protect the core material from the environment outside the microcapsule, but it may also serve as a means of regulating the release of the core material (e.g., fragrance). Thus, the shell may be water-soluble or water-swellable and may initiate fragrance release in response to exposure of the microcapsule to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule may release fragrance in response to elevated temperatures. The microcapsule may also release fragrance in response to shear forces applied to the surface of the microcapsule.

[0196] A preferred type of polymer microparticle suitable for use in the present invention is a polymer core-shell microcapsule in which at least one generally spherical continuous shell of polymer material surrounds a core containing a fragrance preparation (f2). The shell typically accounts for up to 20% by weight, based on the total weight of the microcapsule. The fragrance preparation (f2) typically accounts for about 10 to about 60% by weight, preferably about 20 to about 40% by weight, based on the total weight of the microcapsule. The amount of fragrance (f2) can be determined by taking a slurry of the microcapsules, extracting it into ethanol and measuring it by liquid chromatography.

[0197] The polymer core-shell microcapsules used in the present invention can be prepared using methods known to those skilled in the art, such as coacervation, interfacial polymerization and polycondensation.

[0198] The coacervation process generally involves encapsulating a core material, which is usually insoluble in water, by precipitating a colloidal material onto the surface of a droplet of material. Coacervation can be simple, for example, using one colloid, such as gelatin, or complex, where two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled conditions of pH, temperature and concentration.

[0199] Interfacial polymerization is usually carried out with the formation of a fine dispersion of oil droplets (oil droplets containing core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsule, and the size of the dispersed droplets directly determines the size of the subsequent microcapsules. The microcapsule shell forming material (monomer or oligomer) is contained in the dispersed phase (oil droplets) and the aqueous continuous phase, and they react together at the phase interface to build a polymer wall around the oil droplets, thereby encapsulating the droplets and forming a core-shell microcapsule. An example of a core-shell microcapsule prepared by this method is a polyurea microcapsule with a shell formed by the reaction of a diisocyanate or polyisocyanate with a diamine or polyamine.

[0200] The polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of a precondensate of the polymer material under appropriate stirring conditions to produce capsules of the desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, thereby causing the condensate to separate from the solution and surround the dispersed core material to produce a coacervate film and the desired microcapsules. Examples of core-shell microcapsules prepared by this method are aminoplast microcapsules having a shell formed from the polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde. Suitable crosslinking agents (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) may also be used, and second wall polymers such as polymers and copolymers of acid anhydrides and their derivatives, particularly maleic anhydride, may also be used appropriately.

[0201] An example of a preferred polymer core-shell microcapsule for use in the present invention is an aminoplast microcapsule having an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably, this aminoplast shell is formed from a polycondensation product of melamine and formaldehyde.

[0202] Polymer microparticles suitable for use in the present invention typically have an average particle size of 100 nanometers to 50 microns. Particles larger than this size enter the visible range. Examples of particles in the submicron range include latexes and microemulsions with a typical size range of 100 to 600 nanometers. The preferred particle size range is in the micrometer range. Examples of particles in the micrometer range include polymer core-shell microcapsules (such as those further described above), with a typical size range of 1 to 50 microns, preferably 5 to 30 microns. The average particle size can be determined by light scattering using a Malvern Mastersizer, where the average particle size is considered to be the median particle size D (0.5) value. The particle size distribution can be narrow, wide or multimodal. If desired, the initially produced microcapsules can be filtered or sieved to produce a product with greater size uniformity.

[0203] Polymer microparticles suitable for use in the present invention may be provided with a deposition aid on the outer surface of the microparticle. The deposition aid is used to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate. Desired substrates include cellulose (including cotton) and polyester (including those used to make polyester fabrics).

[0204] The deposition aid may be suitably provided on the outer surface of the microparticle by covalent bonding, entanglement or strong adsorption. Examples include polymer core-shell microcapsules (such as those described further above) in which the deposition aid is preferably attached to the exterior of the shell by covalent bonding. Although it is preferred that the deposition aid is directly attached to the exterior of the shell, it may also be attached via a linking substance.

[0205] The deposition aid for use in the present invention may be suitably selected from polysaccharides having an affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an inherent affinity for cellulose or may be derivatized or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked beta glycan (broadly defined) backbone structure having at least 4, and preferably at least 10, beta 1-4 linked backbone residues, such as a glucan backbone (consisting of beta 1-4 linked glucose residues), a mannan backbone (consisting of beta 1-4 linked mannose residues) or a xylan backbone (consisting of beta 1-4 linked xylose residues). Examples of such beta 1-4 linked polysaccharides include xyloglucans, glucomannans, mannans, galactomannans, beta (1-3), (1-4) glucans and the xylan family including glucuronic acid-, arabinose- and glucuronic acid arabinoxylans. Preferred β1-4 linked polysaccharides for use in the present invention can be selected from plant-derived xyloglucans, such as pea xyloglucan and tamarind xyloglucan (TXG) (which have a β1-4 linked glucan backbone with side chains of α-D-xylopyranose and β-D-galactopyranosyl-(1-2)-α-D-xylopyranose, both linked 1-6 to the backbone); and plant-derived galactomannans, such as locust bean gum (LBG) (which have a mannan backbone of β1-4 linked mannose residues with single unit galactose side chains linked α1-6 to the backbone).

[0206] Also suitable are polysaccharides which upon hydrolysis acquire an affinity for cellulose, such as cellulose monoacetate, or modified polysaccharides having an affinity for cellulose, such as hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl guar, hydroxyethyl ethyl cellulose and methyl cellulose.

[0207] The deposition aid for use in the present invention may also be selected from phthalate-containing polymers having an affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments containing oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments containing terephthalate groups. Typically, the degree of polymerization of the oxyalkylene groups is from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. Suitable examples of phthalate-containing polymers of this type are copolymers having random blocks of ethylene terephthalate and polyoxyethylene terephthalate.

[0208] Mixtures of any of the above materials may also be suitable.

[0209] The deposition aids used in the present invention generally have a weight average molecular weight (MW) ranging from about 5 kDa to about 500 kDa, preferably from about 10 kDa to about 500 kDa, and more preferably from about 20 kDa to about 300 kDa. w ).

[0210] An example of a particularly preferred polymer core-shell microcapsule for use in the present invention is an aminoplast microcapsule having a shell formed by polycondensation of melamine and formaldehyde; surrounding a core containing the fragrance formulation (f2); wherein the deposition aid is attached to the outside of the shell by covalent bonding. Preferred deposition aids are selected from β1-4 linked polysaccharides, in particular xyloglucans of plant origin, as further described above.

[0211] The inventors have surprisingly observed that the total level of fragrance contained in the compositions of the present invention can be reduced without sacrificing the overall fragrance experience delivered to the consumer at a critical stage in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.

[0212] Therefore, the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the concentrated laundry composition of the present invention is suitably in the range of 0.5 to 1.4%, preferably 0.5 to 1.2%, more preferably 0.5 to 1%, most preferably 0.6 to 0.9% (by weight based on the total weight of the concentrated laundry composition).

[0213] The weight ratio of fragrance preparation (f1) to fragrance preparation (f2) in the composition of the present invention is preferably in the range of 60:40 to 45:55. Particularly good results are obtained when the weight ratio of fragrance preparation (f1) to fragrance preparation (f2) is about 50:50.

[0214] Fragrance (f1) and fragrance (f2) are usually incorporated at different stages of the formation of the composition of the present invention. Typically, discrete polymer microparticles (e.g. microcapsules) encapsulating the fragrance formulation (f2) are added as a slurry to a warm base formulation containing the other components of the composition (e.g. surfactants and solvents). Fragrance (f1) is usually post-added later, after the base formulation has cooled.

[0215] Other Ingredients

[0216] The composition may contain further optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include foam boosters, polyelectrolytes, shrink-resistant agents, wrinkle-resistant agents, antioxidants, sunscreens, corrosion inhibitors, drape-imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or sunscreens. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are included individually in an amount of up to 5%, based on the gross weight of the composition.

[0217] Many of the ingredients used in embodiments of the present invention can be obtained from so-called black carbon sources or more sustainable green sources. Provided below is a list of alternative sources for several of these ingredients and how to make them into the feedstocks described herein.

[0218] SLES and PAS

[0219] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are generally obtainable by sulfating alcohol ethoxylates. These alcohol ethoxylates are generally obtainable by ethoxylating linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating the linear alcohols. Thus, the formation of linear alcohols is a central step in obtaining both PAS and alkali metal alkyl ether sulfate surfactants.

[0220] Linear alcohols suitable as an intermediate step in the preparation of alcohol ethoxylates and hence anionic surfactants such as sodium lauryl ether sulfate can be obtained from a number of different sustainable sources. These include:

[0221] Primary sugar

[0222] Primary sugars are obtained from sugar cane or beets, etc., and can be fermented to form bioethanol. The bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form alkenes. These alkenes are then processed into linear alcohols by hydroformylation or oxidation.

[0223] An alternative process can be used that also employs primary sugars to form linear alcohols, and in which the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed to linear fatty acids, which are then reduced to form linear alcohols.

[0224] Biomass

[0225] Biomass, such as forest products, rice husks and straw, can be processed into synthesis gas by gasification. Through the FischerTropsch reaction, these materials are processed into alkanes, which are then dehydrogenated to form alkenes. These alkenes can be treated in the same way as the alkenes described above [primary sugars].

[0226] Another approach is to convert the same biomass into polysaccharides by steam explosion, which can be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which is subsequently dehydrated to form bioethylene. This bioethylene is then processed into linear alcohols as described above [primary sugars].

[0227] Waste Plastics

[0228] Waste plastics are pyrolyzed to form pyrolysis oil. This is then fractionated to form linear alkanes, which are subsequently dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].

[0229] Alternatively, the pyrolyzed oil is cracked to form ethylene which is subsequently processed by olefin metathesis to form the desired alkenes. These are then processed to linear alcohols as described above [primary sugars].

[0230] Municipal solid waste

[0231] MSW is converted to syngas by gasification. From the syngas, it can be processed as described above [primary sugars] or converted to ethanol by an enzymatic process before dehydrogenation to ethylene. The ethylene can then be converted to linear alcohols by the Ziegler process.

[0232] MSW can also be converted to pyrolysis oil by gasification, which is subsequently fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.

[0233] Ocean Carbon

[0234] There are various carbon sources from marine communities such as seaweed and macroalgae. From these marine communities, triglycerides can be isolated from the source and subsequently hydrolyzed to form fatty acids which are reduced to straight chain alcohols in the usual manner.

[0235] Alternatively, the feedstock can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol and then processed as described above [primary sugars].

[0236] Waste oil

[0237] Waste oils, such as used cooking oils, can be physically separated into triglycerides, which are broken down to form straight chain fatty acids and then straight chain alcohols as described above.

[0238] Alternatively, used cooking oil can be subjected to the Neste process, whereby the oil is catalytically cracked to form bio-ethylene. It is then processed as described above.

[0239] Methane capture

[0240] Methane capture processes capture methane from landfills or fossil fuel production. Methane can be formed into synthesis gas by gasification. The synthesis gas can be processed as described above, whereby the synthesis gas is converted to methanol (Fischer Tropsch reaction), then to olefins, and then to linear alcohols by hydroformylation oxidation.

[0241] Alternatively, the synthesis gas can be converted to alkanes and then to olefins via Fischer Tropsch and subsequent dehydrogenation.

[0242] Carbon capture

[0243] Carbon dioxide can be captured by any of a variety of methods that are well known. Carbon dioxide can be converted to carbon monoxide by the reverse water gas shift reaction, which can then be converted to synthesis gas using hydrogen in an electrolysis reaction. The synthesis gas is then processed as described above and converted to methanol and / or alkanes before reacting to form olefins.

[0244] Alternatively, the captured carbon dioxide is mixed with hydrogen before enzymatic processing to form ethanol. This is the process developed by Lanzatech. Thus, ethanol is converted to ethylene, then processed to olefins and then to linear alcohols as described above.

[0245] The above process can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0246] Packaging and dosing

[0247] The composition can be formulated into any suitable physical form, including powder, granules, tablets, liquids, etc. Preferably, the composition is provided in liquid form. More preferably, the composition is a liquid detergent composition, such as a liquid laundry composition or a liquid dishwashing composition, and even more preferably, the composition is a liquid laundry composition.

[0248] The composition of the invention may be supplied in a multi-dose plastic package with a top or bottom closure. The dosing device may be provided as part of the lid or as an integrated system with the package.

[0249] Alternatively, the composition of the present invention can be packaged in a unit dose in a polymer film that is soluble in wash water. The unit dose composition of the present invention is contained in a pouch formed by a water-soluble film. Preferably, the pouch has one to four compartments. More preferably, the pouch has three compartments. It is preferred that the pouch is a unit dose product and can be 10 to 50 g weight to represent a unit dose.

[0250] Such water-soluble film compositions, optional ingredients for use therein, and methods for their preparation are well known in the art, whether for use in preparing relatively thin water-soluble films (eg, as pouch materials) or otherwise.

[0251] In one class of embodiments, the water-soluble film comprises a water-soluble material. Preferred such materials include polyvinyl alcohol (PVOH), including homopolymers thereof (e.g., substantially only vinyl alcohol and vinyl acetate monomer units) and copolymers thereof (e.g., in addition to vinyl alcohol and vinyl acetate units, one or more other monomer units). PVOH is a synthetic resin typically prepared by alcoholysis (commonly referred to as hydrolysis or saponification) of polyvinyl acetate. Fully hydrolyzed PVOH (in which almost all acetate groups are converted to alcohol groups) is a highly crystalline polymer with strong hydrogen bonding that is only soluble in hot water above about 140 degrees Fahrenheit (60°C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, the PVOH polymer is referred to as partially hydrolyzed, with weaker hydrogen bonding and lower crystallinity, and is soluble in cold water below about 50 degrees Fahrenheit (10°C). Intermediate cold or hot water soluble films may include, for example, moderately partially hydrolyzed PVOH (e.g., having a degree of hydrolysis of about 94% to about 98%), and only readily soluble in warm water - e.g., rapidly dissolving at temperatures of about 40 degrees Celsius and above. Fully and partially hydrolyzed PVOH types are often referred to as PVOH homopolymers, although partially hydrolyzed types are technically vinyl alcohol-vinyl acetate copolymers.

[0252] The degree of hydrolysis (DH) of the PVOH polymers and PVOH copolymers included in the water-soluble films of the present disclosure may range from about 75% to about 99% (e.g., from about 79% to about 92%, from about 86.5% to about 89%, or about 88%, such as for cold water soluble compositions; from about 90% to about 99%, from about 92% to about 99%, or from about 95% to about 99%). As the degree of hydrolysis decreases, films made from the resin have reduced mechanical strength but faster solubility at temperatures below about 20°C. As the degree of hydrolysis increases, films made from the polymer tend to be mechanically stronger and thermoformability tends to decrease. The degree of hydrolysis of the PVOH can be selected so that the water solubility of the polymer is temperature dependent, and thus the solubility of the film made from the polymer, any compatibilizing polymers, and additional ingredients is also affected. In one option, the film is cold water soluble. Cold water soluble films soluble in water at a temperature of less than 10 degrees Celsius may include PVOH having a degree of hydrolysis in the range of about 75% to about 90%, or in the range of about 80% to about 90%, or in the range of about 85% to about 90%. In another alternative, the film is hot water soluble. Hot water soluble films soluble in water at a temperature of at least about 60 degrees Celsius may include PVOH having a degree of hydrolysis of at least about 98%.

[0253] In addition to the PVOH polymer and PVOH copolymer in the blend, other water-soluble polymers used may include but are not limited to modified polyvinyl alcohol, polyacrylate, water-soluble acrylate copolymer, polyvinyl pyrrolidone, polyethylene imine, pullulan, water-soluble natural polymers (including but not limited to guar gum, gum arabic, xanthan gum, carrageenan and starch), water-soluble polymer derivatives (including but not limited to modified starch, ethoxylated starch and hydroxypropylated starch), the aforementioned copolymers and any aforementioned combinations. Other water-soluble polymers may also include polyalkylene oxide, polyacrylamide, polyacrylic acid and its salt, cellulose, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polycarboxylic acid and its salt, polyamino acid, polyamide, gelatin, methylcellulose, carboxymethylcellulose and its salt, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin and polymethacrylate. Such water-soluble polymers, whether PVOH or other, can be commercially available from a variety of sources. Any of the aforementioned water-soluble polymers are generally suitable for use as film-forming polymers. Generally speaking, the water-soluble film may include copolymers and / or blends of the aforementioned resins.

[0254] Water-soluble polymers (e.g., PVOH resin blends alone or in combination with other water-soluble polymers) may be included in the film in an amount ranging from, for example, about 30% by weight or 50% by weight to about 90% by weight or 95% by weight. The weight ratio of the amount of all water-soluble polymers to the combined amount of all plasticizers, compatibilizers, and minor additives may be, for example, in the range of about 0.5 to about 18, about 0.5 to about 15, about 0.5 to about 9, about 0.5 to about 5, about 1 to 3, or about 1 to 2. The specific amounts of plasticizers and other non-polymer components may be selected in a particular embodiment based on the intended application of the water-soluble film to adjust the film flexibility and impart processing benefits taking into account the desired mechanical film properties.

[0255] The water-soluble polymers used in the films described herein (including but not limited to PVOH polymers and PVOH copolymers) can be characterized by, for example, a viscosity in the range of about 3.0 to about 27.0 cP, about 4.0 to about 24.0 cP, about 4.0 to about 23.0 cP, about 4.0 cP to about 15 cP, or about 6.0 to about 10.0 cP. As described in the British standard EN ISO 15023-2:2006 Appendix E Brookfield test method, the viscosity of the polymer is determined by measuring a freshly prepared solution using a Brookfield LV type viscometer with a UL adapter. The international practice is to give the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20 degrees Celsius. Unless otherwise stated, the polymer viscosity specified in cP herein should be understood to refer to the viscosity of a 4% aqueous solution of a water-soluble polymer at 20 degrees Celsius.

[0256] It is well known in the art that the viscosity of a water-soluble polymer (PVOH or otherwise) is related to the weight average molecular weight (W) of the same polymer, and viscosity is often used as a proxy for Mw. Thus, the weight average molecular weight of the water-soluble polymer comprising the first PVOH copolymer and the second PVOH polymer may range, for example, from about 30,000 to about 175,000, or from about 30,000 to about 100,000, or from about 55,000 to about 80,000.

[0257] The water-soluble film may contain other auxiliary agents and processing agents, such as but not limited to plasticizers, plasticizers and extenders, surfactants, lubricants, mold release agents, fillers, extenders, crosslinking agents, anti-caking agents, antioxidants, anti-adhesive agents, defoaming agents, nanoparticles (such as layered silicate nanoclays (e.g., sodium montmorillonite)), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite, etc.), aversive agents such as bittering agents (e.g., denatonium salts, such as denatonium benzoate, denatonium sugar and denatonium hydrochloride; sucrose octaacetate; quinine; flavonoids, such as quercetin and naringenin; and bitter substances, such as quassin and strychnine) and stimulants (e.g., capsaicin, piperine, allyl isothiocyanate and resinferatoxin) and other functional ingredients, in amounts suitable for their intended purposes. An embodiment including a plasticizer is preferred. The amount of these agents may be up to about 50%, 20%, 15%, 10%, 5%, 4% and / or at least 0.01%, 0.1%, 1% or 5% by weight, individually or collectively.

[0258] Plasticizer can include but is not limited to glycerine, diglycerine, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol at most 400MW, neopentyl glycol, trimethylolpropane, polyether polyol, sorbitol, 2-methyl-1,3-propylene glycol, ethanolamine and its mixture.Preferred plasticizer is glycerine, sorbitol, triethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propylene glycol, trimethylolpropane or its combination.Based on total film weight, the total amount of plasticizer can be in the range of about 10 weight % to about 40 weight %, or about 15 weight % to about 35 weight %, or about 20 weight % to about 30 weight %, for example, about 25 weight %.The combination of glycerine, dipropylene glycol and sorbitol can be used.Optionally, glycerine can be used with about 5 weight % to about 30 weight %, or 5 weight % to about 20 weight %, for example, about 13 weight % amount.

[0259] Optionally, dipropylene glycol can be used with about 1 % by weight to about 20 % by weight, or about 3 % by weight to about 10 % by weight, for example, 6 % by weight. Optionally, sorbitol can be used with about 1 % by weight to about 20 % by weight, or about 2 % by weight to about 10 % by weight, for example, about 5 % by weight. In a particular embodiment, the specific amount of plasticizer can be selected based on the required film flexibility and processability characteristics of the water-soluble film. Under low plasticizer content, the film may become brittle, difficult to process or be easy to break. Under the plasticizer level that rises, the film may be too soft, weak or difficult to process for desired purposes.

[0260] In a preferred embodiment, the composition comprises a taste aversive (eg, denatonium benzoate) and / or a stimulant (eg, capsaicin).

[0261] Example

[0262] Example 1

[0263] Material

[0264] Protease: Carnival Evity 16L

[0265] Amylase: Amplify Prime 100L

[0266] Lipase: Lipex 100L

[0267] Pectate lyase: Xpect 1000L / T

[0268] Cellulase: Celluclean 5000L

[0269] Cardanol polyoxyethylene ether sulfate: NSN3003 from Nasurfar Biomaterial Technology Co. Ltd

[0270] Preparation of composition

[0271] Surfactants linear alkylbenzene sulfonate (LAS) and cardanol polyoxyethylene ether sulfate (CES) were dissolved in deionized (DI) water to prepare 15 wt % aqueous solutions. Pure DI water was used as a control. All solutions were freshly prepared and checked to ensure that the surfactants were completely dissolved.

[0272] The compositions were prepared by adding various enzymes to the above aqueous solutions. The enzyme dosages are shown in Table 1.

[0273] Table 1

[0274]

[0275]

[0276] Methods for measuring enzyme activity

[0277] Protease activity

[0278] Protease activity is measured by a method using a Suc-AAPF-PNA substrate. Suc-AAPF-PNA is an abbreviation for N-succinyl-alanine-alanine-proline-phenylalanine-p-nitroaniline, and it is a closed peptide that can be cleaved by an endoprotease. After cleavage, the free PNA molecule is released, and it has a yellow color, so it can be measured by visible light spectrophotometry at a wavelength of 405nm. Due to PNA formation, the increase in absorbance is proportional to the activity of the protease in the sample. The reaction is tracked in situ, and the change in absorbance at 405nm per time unit is calculated. The protease activity is automatically calculated by reference to the calibration curve of the corresponding reference standard.

[0279] Amylase activity

[0280] The amylase activity is measured by a method employing the G7-pNP substrate. G7-pNP, which is an abbreviation for 4,6-ethylidene (G7)-p-nitrophenyl (G1)-α, D-maltoheptanoside (ethylidene-G7pNP), is a closed oligosaccharide that can be cleaved by endoamylases such as α-amylases. The hydrolyzed substrate further reacts with α-glucosidase to release free pNP molecules, which have a yellow color and can therefore be measured by visible light spectrophotometry at a wavelength of 405 nm. The increase in absorbance due to pNP formation is proportional to the activity of the amylase in the sample. The reaction is tracked in situ, and the change in absorbance at 405 nm per time unit is calculated. The amylase activity is automatically calculated by reference to a calibration curve of the corresponding reference standard.

[0281] Lipase activity

[0282] The lipase activity is measured by a method employing a p-nitrophenyl acyl ester substrate which can be cleaved by the lipase to release a free p-nitrophenol molecule. The p-nitrophenol molecule has a yellow color and can therefore be measured by visible light spectrophotometry at a wavelength of 405 nm. The increase in absorbance due to the formation of p-nitrophenol is proportional to the activity of the lipase in the sample. The reaction is followed in situ and the change in absorbance at 405 nm per time unit is calculated. The amylase activity is automatically calculated by reference to a calibration curve of the corresponding reference standard.

[0283] Pectate lyase

[0284] Pectate lyase activity is measured by the method using polygalacturonic acid substrate. Pectate lyase cuts polygalacturonic acid by trans-elimination mechanism. This means that it leaves carbon-carbon double bond for each substrate cutting. This bond has absorption at 235nm, thereby allowing to directly detect the activity of pectate lyase to soluble polygalacturonic acid by measuring the absorbance at this wavelength. The absorbance at 235nm is measured in a microtiter spectrometer (e.g., Molecular Devices, SpectraMAX 190). For all measured values, the absorbance reading is corrected for background absorbance by subtracting the absorbance of the control sample that does not add enzyme operation.

[0285] Cellulase

[0286] Cellulase activity was measured by a method using a carboxymethyl cellulose substrate. The substrate carboxymethyl cellulose was hydrolyzed with cellulase at pH 7.5, 50°C for 30 minutes. The reaction was terminated by an alkaline reagent containing 4-hydroxybenzoyl hydrazide (PAHBAH) and bismuth (which forms a complex with a reducing sugar). Complex formation results in color generation, which can be read by a spectrometer at . The increase in absorbance due to the formation of the complex is proportional to the activity of the cellulase in the sample. The reaction was tracked in situ, and the change in absorbance at 405nm per time unit was calculated. Cellulase activity was automatically calculated by reference to the calibration curve of the corresponding reference standard.

[0287] The enzyme activity of the control after preparation (T0) was set to 100%. The composition was then incubated at 37°C for two weeks, and the residual enzyme activity was measured (relative to the time T0 of the control, the control enzyme activity was set to 100%). The results are shown in Table 2.

[0288] Table 2

[0289]

[0290] The results show that Composition 1 (according to the present invention) provides much better enzyme activity compared to the other compositions, indicating improved enzyme stability under storage conditions.

Claims

1. A composition comprising: a) Anion-modified alkyl and / or alkenylphenol polyoxyalkylene ether represented by formula (I) wherein R1 is a straight or branched alkyl or alkenyl group having 11 to 21 carbon atoms; each R2 is an oxyalkylene group having 2 to 4 carbon atoms; m is an integer from 1 to 50; E is a group comprising one or more of sulfate, phosphate, carboxylate, sulfonate, sulfosuccinate, sulfoacetate, sarcosinate and phosphonate; M is a solubilizing cation selected from sodium, potassium, ammonium, monoalkanolamine, dialkanolamine, trialkanolamine and mixtures thereof; and b) Enzymes.

2. The composition according to claim 1, wherein R1 is a straight chain or branched alkyl or alkenyl group having 13 to 17 carbon atoms, preferably a straight chain alkyl or alkenyl group having 13 to 17 carbon atoms.

3. A composition according to claim 1 or claim 2, wherein R1 is a straight chain C15 alkyl or alkenyl group, preferably a straight chain C15 alkyl or alkenyl group containing 0 to 3 carbon-carbon double bonds.

4. A composition according to any preceding claim wherein each R2 is an oxyethylene group.

5. A composition according to any preceding claim, wherein m is an integer from 1 to 30, preferably from 2 to 15, more preferably from 3 to 10.

6. The composition according to any one of the preceding claims, wherein the anionically modified alkyl and / or alkenylphenol polyoxyalkylene ether is anionically modified cardanol polyoxyethylene ether.

7. A composition according to any one of the preceding claims, wherein the anionically modified alkyl and / or alkenylphenol polyoxyethylene ether is cardanol polyoxyethylene ether sulfate, cardanol polyoxyethylene ether phosphate or a mixture thereof, preferably cardanol polyoxyethylene ether sulfate.

8. A composition according to any preceding claim, wherein the enzyme comprises a protease, a lipase, an amylase, a mannanase, a pectate lyase, a cellulase, a phospholipase, a cutinase, a peroxidase, an oxidase or a mixture thereof.

9. A composition according to any preceding claim, wherein the composition comprises the anionically modified alkyl and / or alkenylphenol polyoxyalkylene ether in an amount of from 0.1% to 30%, preferably from 0.5% to 20% by weight of the composition.

10. A composition according to any preceding claim, wherein the composition comprises the enzyme in an amount of from 0.00001% to 1%, preferably from 0.0001% to 0.5%.

11. A composition according to any preceding claim, wherein the composition further comprises a linear alkylbenzene sulfonate.

12. A composition according to any preceding claim, wherein the composition is substantially free of alkyl ether sulfates.

13. A composition according to any preceding claim, wherein the composition is a detergent composition, preferably a liquid detergent composition, more preferably a liquid laundry detergent composition.

14. A composition according to any preceding claim, wherein the composition is in unit dosage form.

15. A method of forming a liquid detergent composition or wash liquor by dispersing a dose of a composition according to any preceding claim in water.

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