Free-flowing solid particulate laundry detergent composition

Abstract

The present invention relates to a free-flowing solid particulate laundry detergent composition wherein the composition comprises a detersive surfactant, an iron-based bleach catalyst and a peroxy-based bleach and the composition has an equilibrium pH of 10.0 or less in deionized water at a concentration of 10 g / l at 20 DEG C.

Description

Technical Field

[0001] The present invention relates to a free-flowing solid granular laundry detergent composition. The composition of the present invention comprises a detersive surfactant, a specific iron-based bleaching catalyst and a peroxy bleach. The composition of the present invention provides good cleaning performance, especially good cleaning performance on curry stains. Background Art

[0002] The feeling of the consumer to laundry detergent powder is that, compared with other laundry detergent product forms such as laundry detergent liquid and laundry detergent pouch, they deliver excellent cleaning performance. For this reason, the cleaning performance of laundry detergent powder needs to be very good. A very good way to ensure that the cleaning performance of laundry detergent powder is very good is to ensure that the stain removal performance of product is very good. The stubborn stain to be removed comprises curry stain. Not only good stain removal performance is important for overall cleaning performance, but this is also one of the main signals that the product has good cleaning performance for consumers. The detergent powder that can remove curry stain well prompts consumers to accept that the overall cleaning performance of laundry detergent powder is good.

[0003] Laundry detergent powder is usually highly alkaline, has a pH distribution of about 10.5, and is usually buffered to this pH distribution by sodium carbonate. This level of alkalinity provides good cleaning, and is one of the main reasons why laundry detergent powder has excellent cleaning performance compared with product forms such as liquids and pouches that usually have a lower pH distribution. However, recently, detergent manufacturers have begun to consider changing this high alkaline pH distribution of laundry detergent powder, and they are trying to prepare a laundry detergent powder with a lower pH distribution and not buffered to this high alkalinity by sodium carbonate. The reason for studying other lower pH distributions is to observe whether other performance vectors such as fabric care, freshness, sanitation, etc. can be significantly improved by being transferred to these new lower pH distributions. However, reducing the pH distribution of laundry detergent compositions tends to skew its cleaning performance distribution, which in turn tends to affect the acceptance of consumers having good cleaning performance to it. Some stains such as curry stains are pH sensitive, and what is particularly problematic is that stains are more difficult to remove at low pH compared to high pH. In other words, the effect of changing pH is not only the effect of the pH environment on the chemicals incorporated into the laundry detergent powder (such as surfactants, bleach, etc.), but also the effect of the pH environment on the stain itself.

[0004] Therefore, there is a need to provide a laundry detergent powder having a low pH profile which still provides good cleaning performance and provides a good signal to the consumer that the cleaning performance is good, such as by having very good stain removal performance on curry stains.

[0005] The present inventors have found that a specific iron-based bleach catalyst (known as FeONIX) provides excellent curry stain removal performance when combined with a peroxy bleach at low pH. The curry stain removal performance is actually enhanced at low pH profiles compared to high pH profiles.

[0006] While other iron-based bleach catalysts are also known, such as FeONIX-A (the amine variant of FeONIX), these bleach catalysts are complex and expensive to synthesize.FeONIX bleach catalysts are more likely to be commercially suitable for laundry detergent powder applications and are a particular focus of laundry detergent manufacturers. Summary of the invention

[0007] The present invention provides a free-flowing solid granular laundry detergent composition, wherein the composition comprises:

[0008] (a) detersive surfactants;

[0009] (b) an iron-based bleach catalyst having the following structure:

[0010] and

[0011] (c) peroxy bleaches,

[0012] wherein the composition has an equilibrium pH of 10.0 or less at a concentration of 10 g / l in deionized water at 20°C. DETAILED DESCRIPTION

[0013] A free-flowing solid granular laundry detergent composition. The composition is a free-flowing solid granular laundry detergent composition. The composition comprises:

[0014] (a) detersive surfactants;

[0015] (b) an iron-based bleach catalyst having the following structure:

[0016] and

[0017] (c) Peroxy bleach.

[0018] The composition has an equilibrium pH of 10.0 or less, preferably less than 10.0, or less than 9.5, or less than 9.0, or less than 8.5, preferably from 6.0 to 10.0, or from 6.0 to 9.5, or from 6.0 to 9.0, or from 6.0 to 8.5 at a concentration of 10 g / l in deionized water at 20°C.

[0019] Preferably, the composition is substantially free of sodium carbonate. "Substantially free" generally means that sodium carbonate is not intentionally included in the composition. However, trace levels (e.g., due to impurities and / or contamination) may be present in the composition, although this is preferably avoided. Typically, if present, the level of any sodium carbonate is less than 2.0% by weight of the composition, preferably less than 1.0% by weight, more preferably less than 0.5% by weight, or even less than 0.1% by weight.

[0020] Preferably, the composition comprises an anionic detersive surfactant. Suitable anionic detersive surfactants are described in more detail below. Preferably, the composition comprises an anionic detersive surfactant selected from alkyl sulfates and / or alkylbenzene sulfonates. Preferred alkyl sulfates are C8-C 24 Alkyl sulfates, particularly preferably mid-cut alkyl sulfates (MCAS), such as C 12 -C 14 Alkyl sulfate. Preferred alkylbenzene sulfonates are C 11 -C 13 Alkylbenzene sulfonate, particularly preferably linear C 11 -C 13 Alkylbenzene sulfonate.

[0021] Preferably, the composition comprises a dye transfer inhibiting agent. Suitable dye transfer inhibiting agents are described in more detail below.

[0022] Preferably, the composition comprises a nonionic detersive surfactant. Suitable nonionic detersive surfactants are described in more detail below.

[0023] Preferably, the composition comprises a hueing dye. Suitable hueing dyes are described in more detail below.

[0024] Preferably, the composition comprises a chelating agent. Suitable chelating agents are described in more detail below.

[0025] Preferably, the composition comprises an enzyme. Suitable enzymes are described in more detail below.

[0026] Preferably, the composition comprises a fragrance. Suitable fragrances are described in more detail below.

[0027] Preferably, the composition comprises a soil release polymer. Suitable soil release polymers are described in more detail below.

[0028] Preferably, the composition comprises:

[0029] (a) 8 wt % to 60 wt % of a detersive surfactant; and

[0030] (b) 0.001 wt% to 1.0 wt% of an iron-based bleach catalyst.

[0031] Preferred ranges for other suitable ingredients are provided below:

[0032] (c) 1.0 wt % to 40 wt %, or 4.0 wt % to 20 wt % of citric acid.

[0033] (d) 0.1% to 5.0% by weight of a dye transfer inhibiting agent.

[0034] (e) 0.5 to 10 wt. % of a nonionic detersive surfactant.

[0035] (f) 0 wt% to 5.0 wt%, or more than 0 wt% to 2.0 wt% of a hueing dye.

[0036] (g) 0.2 to 5.0 wt % of a chelating agent.

[0037] (h) 0.1 wt % to 5.0 wt % enzyme.

[0038] (i) 0.1 wt% to 5.0 wt% of fragrance.

[0039] (j) 0.1 to 10 wt% of a soil release polymer.

[0040] Preferably, the composition comprises an imine-based bleach catalyst and / or an iminium-based bleach catalyst. Typically, the free-flowing solid particulate laundry detergent composition is a fully formulated laundry detergent composition rather than a portion thereof (such as a spray-dried, extruded or agglomerated particle forming only part of a laundry detergent composition). Typically, the solid composition comprises a plurality of chemically distinct particles, such as spray-dried base detergent particles and / or agglomerated base detergent particles and / or extruded base detergent particles; one or more, typically two or more, or five or more, or even ten or more particles are combined, the particles being selected from: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant faces, surfactant flakes; phosphate particles; zeolite particles; silicate particles, especially sodium silicate particles; carbonate particles, especially sodium carbonate particles; polymer particles, such as carboxylate polymer particles, cellulose polymer particles, starch particles, polyester particles, polyamine particles, terephthalic acid polymer particles, polyethylene glycol particles; aesthetic particles, such as colored strips, needles, lamellar particles and ring particles; enzyme particles, such as protease particles, amylase particles, lipase particles, cellulase particles, mannanase particles, pectate lyase particles, xyloglucanase particles, bleaching enzyme particles and any of these enzymes; a co-granule, preferably the enzyme granules comprise sodium sulfate; bleaching agent granules, such as percarbonate granules, especially coated percarbonate granules, such as percarbonate coated with carbonate, sulfate, silicate, borosilicate, or any combination thereof, perborate granules, bleach activator granules such as tetraacetylethylenediamine granules and / or alkyloxybenzenesulfonate granules, bleach catalyst granules such as transition metal catalyst granules, and / or isoquinolinium bleach catalyst granules, preformed peracid granules, especially coated preformed peracid granules Acid particles; filler particles, such as sulfate particles and chloride particles; clay particles, such as montmorillonite particles and clay and silicone particles; flocculant particles, such as polyethylene oxide particles; wax particles, such as wax agglomerates; silicone particles, brightener particles; dye transfer inhibitor particles; dye fixing agent particles; perfume particles, such as perfume microcapsules and starch encapsulated perfume blend particles, and pro-perfume particles, such as Schiff base reaction product particles; hueing dye particles; chelant particles, such as chelant agglomerates; and any combination thereof.

[0041] Suitable compositions typically comprise detergent ingredients selected from the following: detersive surfactants, such as anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants and amphoteric detersive surfactants; polymers, such as carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers and care polymers; bleaches, such as hydrogen peroxide sources, bleach activators, bleach catalysts and preformed peracids; photobleaches, such as sulfonated zinc phthalocyanine and / or sulfonated aluminum phthalocyanine; enzymes, such as proteases, amylases, cellulases, lipases; zeolite builders; phosphate builders; auxiliary builders, such as citric acid and citrates; carbonates, such as sodium carbonate and sodium bicarbonate; sulfates, such as sodium sulfate; silicates, such as sodium silicate; chloride salts, such as sodium chloride; brighteners; chelating agents; colorants; dye transfer inhibitors; dye fixatives; perfumes; silicones; fabric softeners, such as clays; flocculants, such as polyethylene oxides; suds suppressors; and any combination thereof.

[0042] Suitable compositions may have a low buffering capacity. Such laundry detergent compositions typically have a reserve alkalinity to pH 9.5 of less than 5.0 g NaOH / 100 g. These low buffered laundry detergent compositions typically contain low levels of carbonates.

[0043] Iron-based bleaching catalyst. Iron-based bleaching catalyst has the following structure:

[0044]

[0045] Suitable iron-based bleach catalysts include FeONIX.

[0046] Detersive surfactants: Suitable detersive surfactants include anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants and amphoteric detersive surfactants. Suitable detersive surfactants may be linear or branched, substituted or unsubstituted, and may be derived from petrochemical materials or biomaterials.

[0047] Anionic detersive surfactants: Suitable anionic detersive surfactants include sulfonate detersive surfactants and sulfate detersive surfactants.

[0048] Suitable sulfonate detersive surfactants include methyl sulfonate, alpha olefin sulfonate, alkyl benzene sulfonate, especially alkyl benzene sulfonate, preferably C 10-13Alkylbenzene sulfonate. Suitable alkylbenzene sulfonates (LAS) are available, preferably by sulfonating commercially available linear alkylbenzene (LAB); suitable LABs include lower 2-phenyl LABs, other suitable LABs include higher 2-phenyl LABs, such as those sold under the trade name Those supplied by Sasol.

[0049] Suitable sulfate detersive surfactants include alkyl sulfates, preferably C 8-18 Alkyl sulfates, or mainly C 12 Alkyl sulfate.

[0050] Preferred sulfate detersive surfactants are alkyl alkoxylated sulfates, preferably alkyl ethoxylated sulfates, preferably C 8-18 Alkyl alkoxylated sulfate, preferably C 8-18 Alkyl ethoxylated sulfate, preferably alkyl alkoxylated sulfate having an average degree of alkoxylation of 0.5 to 20, preferably 0.5 to 10, preferably alkyl alkoxylated sulfate is C 8-18 Alkyl ethoxylated sulfates having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3, and most preferably from 0.5 to 1.5.

[0051] The alkyl sulfates, alkyl alkoxylated sulfates, and alkyl benzene sulfonates may be linear or branched, substituted or unsubstituted, and may be derived from petrochemical or biomaterials.

[0052] Other suitable anionic detersive surfactants include the alkyl ether carboxylates.

[0053] Suitable anionic detersive surfactants may be in the form of salts, and suitable counterions include sodium, calcium, magnesium, amino alcohols, and any combination thereof. The preferred counterion is sodium.

[0054] Nonionic detersive surfactant: Suitable nonionic detersive surfactants are selected from the group consisting of: C8-C 18 Alkyl ethoxylates, such as those available from Shell Nonionic surfactant; C6-C 12 Alkylphenol alkoxylates, wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units, or mixtures thereof; C 12 -C 18 Alcohol and C6-C 12 Condensates of alkylphenols with ethylene oxide / propylene oxide block polymers, such as those available from BASF Alkyl polysaccharides, preferably alkyl polyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether-terminated poly(alkoxylated) alcohol surfactants; and mixtures thereof.

[0055] Suitable nonionic detersive surfactants are alkyl polyglucosides and / or alkyl alkoxylated alcohols.

[0056] Suitable nonionic detersive surfactants include alkyl alkoxylated alcohols, preferably C 8-18 Alkyl alkoxylated alcohol, preferably C 8-18 The alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol, has an average degree of alkoxylation of 1 to 50, preferably 1 to 30, or 1 to 20, or 1 to 10, preferably the alkyl alkoxylated alcohol is C 8-18 Alkyl ethoxylated alcohols having an average degree of ethoxylation of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and most preferably 3 to 7. The alkyl alkoxylated alcohols may be linear or branched, and substituted or unsubstituted.

[0057] Suitable nonionic detersive surfactants include those based on secondary alcohols.

[0058] Cationic detersive surfactants: Suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof.

[0059] Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula:

[0060] (R)(R1)(R2)(R3)N + X -

[0061] Wherein R is a linear or branched, substituted or unsubstituted C 6-18 Alkyl or alkenyl moiety, R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, and X is an anion providing electroneutrality, and preferred anions include: halide, preferably chloride; sulfate; and sulfonate.

[0062] Zwitterionic detersive surfactants: Suitable zwitterionic detersive surfactants include amine oxides and / or betaines.

[0063] Polymers: Suitable polymers include carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers, conditioning polymers, and any combination thereof.

[0064] Carboxylate polymer: The composition may comprise a carboxylate polymer such as a maleate / acrylate random copolymer or a polyacrylate homopolymer. Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of 4,000 to 9,000 Da; maleate / acrylate random copolymers having a molecular weight of 50,000 to 100,000 Da, or 60,000 to 80,000 Da.

[0065] Another suitable carboxylate polymer is a copolymer comprising: (i) 50 wt% to less than 98 wt% of structural units derived from one or more monomers containing carboxyl groups; (ii) 1 wt% to less than 49 wt% of structural units derived from one or more monomers containing sulfonate moieties; and (iii) 1 wt% to 49 wt% of structural units derived from one or more types of monomers selected from monomers containing ether bonds represented by formula (I) and (II):

[0066] Formula (I):

[0067]

[0068] Wherein in formula (I), R0 represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, and X represents a number from 0 to 5, provided that when R is a single bond, X represents a number from 1 to 5, and R1 is a hydrogen atom or a C1 to C 20 Organic groups;

[0069] Formula (II)

[0070]

[0071] In formula (II), R0 represents a hydrogen atom or a CH3 group, R represents a CH2 group, a CH2CH2 group or a single bond, X represents a number from 0 to 5, and R1 is a hydrogen atom or a C1 to C 20 Organic group.

[0072] It may be preferred that the polymer has a weight average molecular weight of at least 50 kDa or even at least 70 kDa.

[0073] Soil release polymer: The composition may comprise a soil release polymer. Suitable soil release polymers have a structure as defined by one of the following structures (I), (II) or (III):

[0074] (I)-[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d

[0075] (II)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e

[0076] (III)-[(OCHR 5 -CHR 6 ) c -OR 7 ] f

[0077] in:

[0078] a, b and c are 1 to 200;

[0079] d, e and f are 1 to 50;

[0080] Ar is 1,4-substituted phenylene;

[0081] sAr is 1,3-substituted phenylene substituted at position 5 with SO3Me;

[0082] Me is Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is C1-C 18 Alkyl or C2-C 10 Hydroxyalkyl or mixtures thereof;

[0083] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from H or C1-C 18 n-alkyl or C1-C 18 isoalkyl; and

[0084] R 7 A straight or branched C1-C 18 Alkyl, or straight or branched C2-C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C8-C 30 Aryl, or C6-C 30 Arylalkyl.

[0085] Suitable soil release polymers are available from Clariant as A series of polymers are sold, e.g. SRN240 and SRA300. Other suitable soil release polymers are available from Solvay as A series of polymers are sold, e.g. SF2 and Crystal.

[0086] Anti-redeposition polymers: Suitable anti-redeposition polymers include polyethylene glycol polymers and / or polyethylene imine polymers.

[0087] Suitable polyethylene glycol polymers include random graft copolymers comprising: (i) a hydrophilic backbone comprising polyethylene glycol; and (ii) one or more hydrophobic side chains selected from the group consisting of: C4-C 25 Alkyl groups, polypropylene, polybutylene, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic or methacrylic acid, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone having randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may be in the range of 2,000Da to 20,000Da, or 4,000Da to 8,000Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains may be in the range of 1:1 to 1:5, or 1:1.2 to 1:2. The average number of grafting sites per ethylene oxide unit may be less than 0.02, or less than 0.016, the average number of grafting sites per ethylene oxide unit may be in the range of 0.010 to 0.018, or the average number of grafting sites per ethylene oxide unit may be less than 0.010, or in the range of 0.004 to 0.008.

[0088] Suitable polyethylene glycol polymers are described in WO08 / 007320.

[0089] A suitable polyethylene glycol polymer is Sokalan HP22.

[0090] Cellulosic polymer: Suitable cellulosic polymers are selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose, sulfonate alkyl cellulose, more preferably selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

[0091] Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000 Da to 300,000 Da.

[0092] Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, for example as described in WO 09 / 154933.

[0093] Care polymers: Suitable care polymers include cationically modified or hydrophobically modified cellulosic polymers. Such modified cellulosic polymers can provide anti-abrasion benefits and dye lock benefits to fabrics during the wash cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.

[0094] Other suitable care polymers include dye lock polymers, such as condensation oligomers produced by condensation of imidazole and epichlorohydrin, preferably in a 1:4:1 ratio. Suitable commercially available dye lock polymers are FDI (Cognis).

[0095] Other suitable care polymers include amino-silicones, which can provide fabric feel benefits and fabric form retention benefits.

[0096] Bleaching agents: Typical bleaching agents include a hydrogen peroxide source, a bleach activator, a bleach catalyst, a preformed peracid, and any combination thereof. Particularly typical bleaching agents include a combination of a hydrogen peroxide source and a bleach activator.

[0097] Hydrogen Peroxide Source: Typical hydrogen peroxide sources include sodium perborate and / or sodium percarbonate.

[0098] Bleach Activators: Typical bleach activators include tetraacetylethylenediamine (TAED) and / or alkyloxybenzene sulfonates.

[0099] Preformed Peracids: Typical preformed peracids include phthalimidyl-peroxycaproic acid.

[0100] Enzymes: Suitable enzymes include lipases, proteases, cellulases, amylases, and any combination thereof.

[0101] Proteases: Suitable proteases include metalloproteases and serine proteases. Examples of suitable neutral or alkaline proteases include: subtilisin (EC 3.4.21.62); trypsin-type or chymotrypsin-type proteases; and metalloproteases. Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.

[0102] Suitable commercially available proteases include those sold under the trade names Liquanase Savinase and Those sold by Novozymes A / S (Denmark); under the trade name A series of proteases, including P280, P281, P2018-C, P2081-WE, P2082-EE and P2083-A / J, Purafect Purafect and Purafect Those sold by DuPont; under the trade name and Those sold by Solvay Enzymes; those purchased from Henkel / Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604, with the following mutations: S99D+S101 R+S103A+V104I+G159S, hereinafter referred to as BLAP); BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D), all from Henkel / Kemira; and KAP (alkalophilic Bacillus subtilisin with mutations A230V+S256G+S259N) from Kao.

[0103] Suitable proteases are described in WO11 / 140316 and WO11 / 072117.

[0104] Amylase: Suitable amylases are derived from AA560 alpha amylase endogenous to Bacillus sp. DSM 12649, preferably with the following mutations: R118K, D183*, G184*, N195F, R320K and / or R458K. Suitable commercially available amylases include Plus, Natalase, Ultra, SZ, (both from Novozymes) and AA, Preferenz Series of amylase, and Ox Am, HT Plus (both from Du Pont).

[0105] Suitable amylases are described in WO06 / 002643.

[0106] Cellulase: Suitable cellulases include those derived from bacteria or fungi. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, such as fungal cellulases produced by Humicola insolens, Myceliophthora thermophila, and Fusarium oxysporum.

[0107] Commercially available cellulases include and Premium, and (Novozymes A / S), Series enzymes (Du Pont), and Series enzymes (AB Enzymes). Suitable commercially available cellulases include Premium, Classic. Suitable proteases are described in WO07 / 144857 and WO10 / 056652.

[0108] Lipase: Suitable lipases include those of bacterial, fungal or synthetic origin, and variants thereof. Chemically modified or protein engineered mutants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces), such as from H. lanuginosa (T. lanuginosus).

[0109] The lipase may be a "first cycle lipase", e.g., such as those described in WO06 / 090335 and WO13 / 116261. In one aspect, the lipase is a first wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus comprising a T231R and / or N233R mutation. Preferred lipases include those sold under the trade name and Those sold by Novozymes (Bagsvaerd, Denmark).

[0110] Other suitable lipases include: Liprl 139, e.g., as described in WO2013 / 171241; and TfuLip2, e.g., as described in WO2011 / 084412 and WO2013 / 033318.

[0111] Other enzymes: Other suitable enzymes are bleaching enzymes such as peroxidases / oxidases, including those of plant, bacterial or fungal origin, and variants thereof. Commercially available peroxidases include (Novozymes A / S). Other suitable enzymes include choline oxidase and perhydrolase, such as used in Gentle Power Bleach TM Those in .

[0112] Other suitable enzymes include those sold under the trade name (from Novozymes A / S, Bagsvaerd, Denmark) and Pectate lyase sold under the trade name (Novozymes A / S, Bagsvaerd, Denmark) and Mannanase sold by Du Pont.

[0113] Zeolite builder: The composition may contain a zeolite builder. The composition may contain from 0% to 5% by weight of a zeolite builder, or 3% by weight of a zeolite builder. The composition may even be substantially free of zeolite builder; substantially free means "no intentionally added". Typical zeolite builders include zeolite A, zeolite P and zeolite MAP.

[0114] Phosphate builder: The composition may contain a phosphate builder. The composition may contain from 0% to 5% by weight of a phosphate builder, or to 3% by weight of a phosphate builder. The composition may even be substantially free of phosphate builders; substantially free means "no intentionally added". A typical phosphate builder is sodium tripolyphosphate.

[0115] Carbonate: The composition may comprise carbonate. The composition may comprise 0 wt% to 10 wt% carbonate, or 0 wt% to 5 wt% carbonate. The composition may even be substantially free of carbonate; substantially free means "no intentionally added". Suitable carbonates include sodium carbonate and sodium bicarbonate.

[0116] Silicate: The composition may comprise a silicate. The composition may comprise 0 to 10 wt% silicate, or 0 to 5 wt% silicate. A preferred silicate is sodium silicate, particularly preferred is sodium silicate having a Na2O:SiO2 ratio of 1.0 to 2.8, preferably 1.6 to 2.0.

[0117] Sulphate: A suitable sulphate is sodium sulphate.

[0118] Brighteners: Suitable fluorescent brighteners include: distyrylbiphenyl compounds, such as CBS-X; diaminostilbene disulfonic acid compounds, such as DMS pure Xtra and HRH; and pyrazoline compounds, e.g. SN; and coumarin compounds, e.g. SWN.

[0119] Preferred brighteners are: sodium 2(4-phenylvinyl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis{[(4-phenylamino-6-(N-methyl-N-2-hydroxyethyl)amino1,3,5-triazine-2-yl)]; amino}stilbene-2-2'disulfonic acid, disodium 4,4'-bis{[(4-phenylamino-6-morpholino-1,3,5-triazine-2-yl)]amino}stilbene-2-2'disulfonic acid and disodium 4,4'-bis(2-sulfonylstyryl)biphenyl. A suitable fluorescent brightener is CI fluorescent brightener 260, which can be used in its β or α crystalline form or a mixture of these crystalline forms.

[0120] Chelating agents: The composition may also contain a chelating agent. Suitable chelating agents may include phosphonates, aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, or mixtures thereof, preferably aminocarboxylates. Chelating agents used herein are not intended to include traditional builders, such as citric acid, although such builders may be present in the compositions of the present disclosure.

[0121] Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetraacetate, N-(hydroxyethyl)ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanolimidodiacetic acid, alkali metal salts, ammonium salts, and substituted ammonium salts thereof, and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when low levels of total phosphorus are permitted; and include ethylenediaminetetra(methylenephosphonates). Polyfunctionally substituted aromatic chelating agents may include catechols, such as sulfonated catechols.

[0122] Suitable chelating agents may include: DTPA (diethylenetriaminepentaacetic acid), HEDP (hydroxyethanediphosphonic acid), EDDS (ethylenediamine disuccinate (EDDS)), DTPMP (diethylenetriaminepenta(methylenephosphonic acid)), EDTMP (ethylenediaminetetra(methylenephosphonic acid)), (1,2-dihydroxybenzene-3,5-disulfonic acid), HPNO (2-pyridinol-N-oxide), MGDA (methylglycine diacetic acid), GLDA (glutamic acid-N,N-diacetic acid), any suitable derivatives thereof, salts thereof, and mixtures thereof.

[0123] Hueing agents: Suitable hueing agents include small molecule dyes, typically belonging to the following Color Index (CI) classifications: acid dyes, direct dyes, basic dyes, reactive dyes (including their hydrolyzed forms), or solvent dyes or disperse dyes, such as dyes classified as blue, violet, red, green or black, and providing the desired hue, alone or in combination. Preferred such hues include acid violet 50, direct violet 9, 66 and 99, solvent violet 13, and any combination thereof.

[0124] Many hueing agents that may be suitable for use in the present invention are known and described in the art, such as the hueing agents described in WO2014 / 089386.

[0125] Suitable hueing agents include phthalocyanine and azo dye conjugates such as described in WO2009 / 069077.

[0126] Suitable toners can be alkoxylated. Such alkoxylated compounds can be prepared by organic synthesis, which can produce a mixture of molecules with different degrees of alkoxylation. Such mixtures can be used directly to provide toners, or can undergo purification steps to increase the ratio of the target molecule. Suitable toners include alkoxylated disazo dyes, such as those described in WO2012 / 054835, and / or alkoxylated thiophene azo dyes, such as those described in WO2008 / 087497 and WO2012 / 166768.

[0127] Toner can be incorporated in the detergent composition as a part for reaction mixture, and this reaction mixture is the result of organic synthesis dye molecules by one or more optional purification steps.This type of reaction mixture generally comprises dye molecules itself, and can also comprise the by product of unreacted parent material and / or organic synthesis pathway in addition.Suitable toner can be incorporated in the hueing dye particles, such as being described in WO 2009 / 069077.

[0128] Dye transfer inhibitors: Suitable dye transfer inhibitors include polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinyl pyrrolidone, polyvinyl oxazolidones, polyvinyl imidazoles and mixtures thereof. Preferred are poly(vinyl pyrrolidone), poly(vinyl pyridine betaine), poly(vinyl pyridine N-oxide), poly(vinyl pyrrolidone-vinylimidazole) and mixtures thereof. Suitable commercially available dye transfer inhibitors include PVP-K15 and K30 (Ashland), HP165, HP50, HP53, HP59, HP56K, HP56, HP66 (BASF), S-400, S403E and S-100 (Ashland).

[0129] Fragrances: Suitable fragrances include fragrance materials selected from the following groups: (a) fragrance materials having a ClogP of less than 3.0 and a boiling point of less than 250°C (Quadrant 1 fragrance materials); (b) fragrance materials having a ClogP of less than 3.0 and a boiling point of 250°C or greater (Quadrant 2 fragrance materials); (c) fragrance materials having a ClogP of 3.0 or greater and a boiling point of less than 250°C (Quadrant 3 fragrance materials); (d) fragrance materials having a ClogP of 3.0 or greater and a boiling point of 250°C or greater (Quadrant 4 fragrance materials); and (e) mixtures thereof.

[0130] For spices, it is preferably in the form of spices delivery technology. Such delivery technology also stabilizes and enhances the release of deposition and spices materials from washed fabrics. Such spices delivery technology can also be used to further increase the persistence of releasing spices from washed fabrics. Suitable spices delivery technology includes: spices microcapsules, former spices, polymer-assisted delivery, molecule-assisted delivery, fiber-assisted delivery, amine-assisted delivery, cyclodextrin, starch encapsulation concoction, zeolite and other inorganic carriers, and any mixture thereof. Suitable spices microcapsules are described in WO2009 / 101593.

[0131] Silicones: Suitable silicones include polydimethylsiloxanes and amino-silicones. Suitable silicones are described in WO05075616.

[0132] Method for preparing the composition: Generally, the particles of the composition can be prepared by any suitable method, such as spray drying, agglomeration, extrusion, and any combination thereof.

[0133] Typically, suitable spray drying methods include the steps of forming an aqueous slurry mixture, transferring the aqueous slurry mixture to a pressure nozzle by at least one pump, preferably two pumps. Atomizing the aqueous slurry mixture into a spray drying tower and drying the aqueous slurry mixture to form spray-dried particles. Preferably, the spray drying tower is a countercurrent spray drying tower, although a cocurrent spray drying tower may also be suitable.

[0134] Typically, the spray-dried powder is subjected to cooling, such as air stripping. Typically, the spray-dried powder is subjected to particle size classification, such as sieving, to obtain a desired particle size distribution. Preferably, the spray-dried powder has a particle size distribution such that the weight average particle size is in the range of 300 microns to 500 microns, and less than 10% by weight of the spray-dried particles have a particle size greater than 2360 microns.

[0135] It may be preferred to heat the aqueous slurry mixture to raise the temperature prior to atomization into a spray drying tower, such as described in WO2009 / 158162.

[0136] For anionic surfactants, such as linear alkylbenzene sulfonates it may be preferred that they are introduced into the spray drying process after the step of forming the aqueous slurry mixture: for example, the acid precursor is introduced into the aqueous slurry mixture after pumping, such as described in WO 09 / 158449.

[0137] It may be preferred for a gas such as air to be introduced into the spray drying process after the step of forming the aqueous slurry, such as described in WO2013 / 181205.

[0138] It may be preferred for any inorganic ingredients, such as sodium sulphate and sodium carbonate, if present in the aqueous slurry mixture, that the sodium sulphate and sodium carbonate are micronised to a small particle size, such as described in WO2012 / 134969.

[0139] Typically, suitable agglomeration processes include the step of contacting a detersive ingredient, such as a detersive surfactant, e.g. linear alkylbenzene sulfonate (LAS) and / or an alkyl alkoxylated sulfate, with an inorganic material, such as sodium carbonate and / or silica in a mixer. The agglomeration process may also be an in-situ neutralization agglomeration process, wherein an acid precursor of a detersive surfactant, such as LAS, is contacted with an alkaline material, such as carbonate and / or sodium hydroxide in a mixer, and wherein the acid precursor of the detersive surfactant is neutralized by the alkaline material during the agglomeration process to form a detersive surfactant.

[0140] Other suitable detergent ingredients that may be agglomerated include polymers, chelating agents, bleach activators, silicones, and any combination thereof.

[0141] Agglomeration process can be high, medium or low shear agglomeration process, wherein high shear, medium shear or low shear mixer is used accordingly. Agglomeration process can be multi-step agglomeration process, wherein two or more mixers are used, such as high shear mixer combined with medium or low shear mixer. Agglomeration process can be continuous process or batch process.

[0142] It may be preferred for the agglomerates to be subjected to a drying step, for example to a fluidized bed drying step. It may also be preferred for the agglomerates to be subjected to a cooling step, for example to a fluidized bed cooling step.

[0143] Typically, the agglomerates are subjected to particle size classification, such as fluidized bed elution and / or sieving, to obtain a desired particle size distribution. Preferably, the agglomerates have a particle size distribution such that the weight average particle size is in the range of 300 microns to 800 microns, and less than 10% by weight of the agglomerates have a particle size of less than 150 microns, and less than 10% by weight of the agglomerates have a particle size greater than 1200 microns.

[0144] It may be preferred for fine and oversized agglomerates to be recycled back into the agglomeration process. Typically, oversized particles are subjected to a comminution step, such as grinding, and recycled back to a suitable location in the agglomeration process, such as a mixer. Typically, fines are recycled back to a suitable location in the agglomeration process, such as a mixer.

[0145] For ingredients, such as polymers and / or nonionic detersive surfactants and / or perfumes, it may be preferred to spray onto base detergent particles, such as spray-dried base detergent particles and / or agglomerated base detergent particles. Typically, the spraying step is carried out in a tumble drum mixer.

[0146] Method for washing fabrics: The method for washing fabrics comprises contacting the composition with water to form a wash liquor, and the step of washing the fabrics in the wash liquor. Typically, the wash liquor has a temperature of from 0°C to 90°C, or to 60°C, or to 40°C, or to 30°C, or to 20°C. The fabric may be contacted with water before, after, or while the solid composition is contacted with water. Typically, the wash liquor is formed by contacting the laundry detergent with water in such an amount that the concentration of the laundry detergent composition in the wash liquor is from 0.2g / L to 20g / L, or from 0.5g / L to 10g / L, or to 5.0g / L. The method for washing fabrics can be carried out in a front-loading automatic washing machine, a top-loading automatic washing machine, including a high-efficiency automatic washing machine, or a suitable hand-washing container. Typically, the wash liquor comprises 90 liters or less, or 60 liters or less, or 15 liters or less, or 10 liters or less of water. Typically, 200 g or less, alternatively 150 g or less, alternatively 100 g or less, alternatively 50 g or less of the laundry detergent composition is contacted with water to form the wash liquor.

[0147] Methods for measuring pH

[0148] Typically, the pH of the composition is measured using an electrode. The composition is diluted to a concentration of 10 g / l in deionized water at 20°C and stirred to dissolve the composition. The pH of the sample is then measured using a pH meter such as an electrode.

[0149] Embodiments of the present invention

[0150] 1. A free-flowing solid granular laundry detergent composition, wherein the composition comprises:

[0151] (a) detersive surfactants;

[0152] (b) an iron-based bleach catalyst having the following structure:

[0153]

[0154] (c) peroxy bleaches,

[0155] wherein the composition has an equilibrium pH of 10.0 or less at a concentration of 1 g / l in deionized water at 20°C.

[0156] 2. A composition according to embodiment 1, wherein the peroxygen bleach is a percarbonate bleach.

[0157] 3. A composition according to embodiment 1, wherein the peroxy bleach is a preformed peroxyacid.

[0158] 4. A composition according to any preceding embodiment, wherein the composition comprises a bleach activator.

[0159] 5. The composition according to any preceding embodiment, wherein the composition comprises tetraacetylethylenediamine.

[0160] 6. A composition according to any preceding embodiment, wherein the composition comprises an imine-based bleach catalyst and / or an iminium-based bleach catalyst.

[0161] 7. A composition according to any preceding embodiment, wherein the composition comprises citric acid.

[0162] 8. A composition according to any preceding embodiment, wherein the composition is substantially free of sodium carbonate.

[0163] 9. The composition according to any preceding embodiment, wherein the composition has an equilibrium pH of less than 8.5 at a concentration of 1 g / l in deionized water at 20°C.

[0164] 10. A composition according to any preceding embodiment, wherein the composition comprises an anionic detersive surfactant.

[0165] 11. A composition according to any preceding embodiment, wherein the composition comprises an anionic detersive surfactant selected from alkyl sulfates and / or alkyl benzene sulfonates.

[0166] 12. A composition according to any preceding embodiment, wherein the composition comprises a dye transfer inhibiting agent.

[0167] 13. A composition according to any preceding embodiment, wherein the composition comprises a non-ionic detersive surfactant.

[0168] 14. The composition according to any preceding embodiment, wherein the composition comprises a hueing dye.

[0169] 15. The composition according to any preceding embodiment, wherein the composition comprises a chelating agent.

[0170] 16. The composition according to any preceding embodiment, wherein the composition comprises an enzyme.

[0171] 17. A composition according to any preceding embodiment, wherein the composition comprises a soil release polymer.

[0172] Example

[0173] The tests were conducted using the following detergent compositions.

[0174]

[0175] Washing method: Each composition was added separately to the tank of an oscillating detergent. The volume of each tank was 1L. The washing temperature was set to 27°C. Throughout the process, 21gpg of water was used. The product was stirred for 1 minute (300rpm), and then the fabric was added (two internal repeats of each stain, and an additional knitted cotton ballast to bring the total fabric weight to 60g). Once the fabric was added, the wash solution was stirred for 17 minutes (208rpm). The wash solution was then drained, and the fabric was subjected to a 5-minute rinse step, then drained and spin-dried. The washed fabric was then dried overnight at 32°C and 80% RH, and then analyzed to measure the stains removed from the fabric. The process was repeated three more times, resulting in a total of four external repeats.

[0176] Stain removal effect analysis: The L*a*b* values ​​of the fabrics were analyzed using the commercially available Verivide DigiEye software. The SRI value was then calculated from the L*a*b* values ​​using the formula shown. The higher the SRI, the better the stain removal effect.

[0177] %SRI (stain removal effect) = 100*((ΔE b –ΔE a ) / ΔE b )

[0178] ΔE b =√((L c -L b ) 2 +(a c -a b ) 2 +b c -b b ) 2 )

[0179] ΔE a =√((L c -L a ) 2 +(a c -a a ) 2 +b c -b a ) 2 )

[0180] Subscript "b" indicates the data of the stain before washing

[0181] Subscript "a" indicates the stain data after washing

[0182] Subscript "c" indicates data for undyed fabrics

[0183] Therefore, L*a*b* values ​​were obtained from undyed fabric, dyed fabric before washing and dyed fabric after washing.

[0184]

[0185] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

1. A free-flowing solid granular laundry detergent composition, wherein the composition comprises: (a) detersive surfactants; (b) an iron-based bleach catalyst having the structure: and (c) peroxy bleaches, wherein the composition has an equilibrium pH of 10.0 or less at a concentration of 10 g / l in deionized water at 20°C.

2. A composition according to claim 1, wherein the peroxy bleach is a percarbonate bleach.

3. The composition of claim 1 wherein the peroxy bleach is a preformed peroxyacid.

4. A composition according to any preceding claim, wherein the composition comprises a bleach activator.

5. A composition according to any preceding claim, wherein the composition comprises tetraacetylethylenediamine.

6. A composition according to any preceding claim, wherein the composition comprises an imine based bleach catalyst and / or an iminium based bleach catalyst.

7. A composition according to any preceding claim, wherein the composition comprises citric acid.

8. A composition according to any preceding claim, wherein the composition is substantially free of sodium carbonate.

9. A composition according to any preceding claim, wherein the composition has an equilibrium pH of less than 8.5 at a concentration of 10 g / l in deionised water at 20°C.

10. A composition according to any preceding claim, wherein the composition comprises an anionic detersive surfactant.

11. A composition according to any preceding claim wherein the composition comprises an anionic detersive surfactant selected from alkyl sulphates and / or alkyl benzene sulphonates.

12. A composition according to any preceding claim, wherein the composition comprises a dye transfer inhibiting agent.

13. A composition according to any preceding claim, wherein the composition comprises a non-ionic detersive surfactant.

14. A composition according to any preceding claim, wherein the composition comprises a hueing dye.

15. A composition according to any preceding claim, wherein the composition comprises a chelating agent.

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