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 sulfite-based reduction bleach.

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 sulfite-based 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 sachets, 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 the product is very good. The stubborn stains to be removed include curry stains and ink stains. 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 stains and ink stains well prompts people to accept that the overall cleaning performance of laundry detergent powder is good.

[0003] Therefore, there is a need to provide a laundry detergent powder which 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 and ink stains.

[0004] One of the best bleaches for removing ink stains is a sulfate-based bleach. Sulfite-based bleaches are reducing bleaches. Their use in laundry detergent powders is very limited because they tend to be incompatible with other bleaching systems, such as peroxy bleaches that are more widely used in laundry detergent powders.

[0005] Incorporation of sulfite based bleaches in laundry detergent systems is not straightforward or simple and compatibility with ingredients, especially bleaching ingredients, requires careful consideration. This is unfortunate because often other bleaching ingredients also provide good stain removal performance on these so called "HERO" stains such as curry stains, which provides a strong signal to consumers, thus promoting consumer acceptance of laundry detergent powders with good overall cleaning performance.

[0006] FeONIX and FeONIX-A are new and emerging bleaching ingredients which are iron based bleach catalysts. They are particularly important to detergent manufacturers as they provide excellent curry stain removal performance, i.e. "HERO" stains, and provide a strong signal and consumer acceptance of laundry detergent powders with good overall cleaning performance.

[0007] The inventors were surprised to find that these new iron-based bleach catalysts (FeONIX and FeONIX-A) are compatible with sulfite bleaches, and the combination of these iron-based bleach catalysts and sulfite-based bleaches provides good stain removal performance on both curry stains and ink stains. This combination provides a very strong and powerful signal to consumers that the laundry detergent powder has excellent overall cleaning performance. Typically, it is expected that iron-based bleach catalysts will impair the performance of sulfite-based bleaches, and sulfite-based bleaches will impair the performance of iron-based catalysts. Unexpectedly and surprisingly, this combination of technologies is compatible with each other and can promote stain removal performance on both "HERO" stains. Summary of the invention

[0008] The present invention provides a free-flowing solid granular laundry detergent composition, wherein the composition comprises:

[0009] (a) detersive surfactants;

[0010] (b) an iron-based bleach catalyst having the structure:

[0011] and

[0012] (c) Sulfite-based reducing bleaches. 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] 1. A free-flowing solid granular laundry detergent composition, wherein the composition comprises:

[0015] (a) detersive surfactants;

[0016] (b) an iron-based bleach catalyst having the structure:

[0017] and

[0018] (c) Sulfite-based reducing bleaches.

[0019] The composition may have 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 6.0 to 10.0, or 6.0 to 9.5, or 6.0 to 9.0, or 6.0 to 8.5 at a concentration of 1 g / l in deionized water at 20°C.

[0020] The composition may have an equilibrium pH of 10.0, or greater than 10.0, preferably greater than 10.5, or even greater than 11.0, preferably from 10.0 to 12.0, or from 10.5 to 12.0, or from 10.5 to 11.5 at a concentration of 1 g / l in deionized water at 20°C.

[0021] The composition may be 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.

[0022] 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 C 8 -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.

[0023] Preferably, the composition comprises a dye transfer inhibiting agent. Suitable dye transfer inhibiting agents are described in more detail below.

[0024] Preferably, the composition comprises a nonionic detersive surfactant. Suitable nonionic detersive surfactants are described in more detail below.

[0025] Preferably, the composition comprises a hueing dye. Suitable hueing dyes are described in more detail below.

[0026] Preferably, the composition comprises a chelating agent. Suitable chelating agents are described in more detail below.

[0027] Preferably, the composition comprises an enzyme. Suitable enzymes are described in more detail below.

[0028] Preferably, the composition comprises a fragrance. Suitable fragrances are described in more detail below.

[0029] Preferably, the composition comprises a soil release polymer. Suitable soil release polymers are described in more detail below.

[0030] Preferably, the composition comprises:

[0031] (a) 8 wt % to 60 wt % of a detersive surfactant; and

[0032] (b) 0.001 wt% to 1.0 wt% of an iron-based bleach catalyst.

[0033] Preferred ranges for other suitable ingredients are provided below:

[0034] (c) 1.0 to 40 wt. % sodium carbonate.

[0035] (d) 0.1% to 5.0% by weight of a dye transfer inhibiting agent.

[0036] (e) 0.5 to 10 wt. % of a nonionic detersive surfactant.

[0037] (f) 0 wt% to 5.0 wt%, or more than 0 wt% to 2.0 wt% of a hueing dye.

[0038] (g) 0.2 to 5.0 wt % of a chelating agent.

[0039] (h) 0.1 wt % to 5.0 wt % enzyme.

[0040] (i) 0.1 wt% to 5.0 wt% of fragrance.

[0041] (j) 0.1 to 10 wt% of a soil release polymer.

[0042] (j) 1.0 to 40 wt % citric acid.

[0043] Typically, the free-flowing solid granular laundry detergent composition is a fully formulated laundry detergent composition, rather than a portion thereof (such as spray-dried, extruded or agglomerated particles that form only a portion of the 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 pasties, 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 streaks, 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 co-particles of any of these enzymes, preferably these enzyme particles contain sodium sulfate; bleaching agent 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.

[0044] Suitable compositions typically comprise detergent ingredients selected from the group consisting of 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; bleach; 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; hueing agents; dye transfer inhibitors; dye fixatives; perfumes; silicones; fabric softeners, such as clays; flocculants, such as polyethylene oxides; suds suppressors; and any combination thereof.

[0045] 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.

[0046] Iron-based bleaching catalyst. Iron-based bleaching catalyst has the following structure:

[0047]

[0048] Suitable iron-based bleach catalysts include FeONIX and / or from Weylchem FeONIX-A.

[0049] Sulfite based reducing bleach.

[0050] The composition comprises a sulphite based reducing bleach. Typically the composition comprises from 0.05 wt% to 15 wt% of a sulphite based reducing bleach.

[0051] Preferably, the sulfite-based reducing bleach is selected from the group consisting of sulfites, bisulfites, dithionites, metabisulfites, and any combination thereof.

[0052] 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.

[0053] Anionic detersive surfactants: Suitable anionic detersive surfactants include sulfonate detersive surfactants and sulfate detersive surfactants.

[0054] Suitable sulfonate detersive surfactants include methyl sulfonate, alpha olefin sulfonate, alkyl benzene sulfonate, especially alkyl benzene sulfonate, preferably C 10-13 Alkylbenzene 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.

[0055] Suitable sulfate detersive surfactants include alkyl sulfates, preferably C 8-18 Alkyl sulfates, or mainly C 12Alkyl sulfate.

[0056] 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.

[0057] 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.

[0058] Other suitable anionic detersive surfactants include the alkyl ether carboxylates.

[0059] 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.

[0060] Nonionic detersive surfactant: Suitable nonionic detersive surfactant is selected from the group consisting of: C 8 -C 18 Alkyl ethoxylates, such as those available from Shell Nonionic surfactant; C 6 -C 12 Alkylphenol alkoxylates, wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units, or mixtures thereof; C 12 -C 18 Alcohol and C 6 -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.

[0061] Suitable nonionic detersive surfactants are alkyl polyglucosides and / or alkyl alkoxylated alcohols.

[0062] Suitable nonionic detersive surfactants include alkyl alkoxylated alcohols, preferably C 8-18 Alkyl alkoxylated alcohol, preferably C 8-18The 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.

[0063] Suitable nonionic detersive surfactants include those based on secondary alcohols.

[0064] 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.

[0065] Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula:

[0066] (R)(R 1 )(R 2 )(R 3 )N + X -

[0067] Wherein R is a linear or branched, substituted or unsubstituted C 6-18 The alkyl or alkenyl moiety, R 1 and R 2 independently selected from a methyl or ethyl moiety, R 3 is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, and X is an anion providing electroneutrality, preferred anions include: halide, preferably chloride; sulfate; and sulfonate.

[0068] Zwitterionic detersive surfactants: Suitable zwitterionic detersive surfactants include amine oxides and / or betaines.

[0069] Polymers: Suitable polymers include carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers, conditioning polymers, and any combination thereof.

[0070] 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.

[0071] 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):

[0072] Formula (I):

[0073]

[0074] Wherein in formula (I), R 0 Represents a hydrogen atom or CH 3 Group, R represents CH 2 Group, CH 2 CH 2 a radical or a single bond, 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 R 1 A hydrogen atom or C 1 To C 20 Organic groups;

[0075] Formula (II)

[0076]

[0077] In formula (II), R 0 Represents a hydrogen atom or CH 3 Group, R represents CH 2 Group, CH 2 CH 2 a radical or a single bond, X represents a number from 0 to 5, and R 1 A hydrogen atom or C 1 To C 20 Organic group.

[0078] It may be preferred that the polymer has a weight average molecular weight of at least 50 kDa or even at least 70 kDa.

[0079] 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):

[0080] (I)-[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d

[0081] (II)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e

[0082] (III)-[(OCHR 5 -CHR 6 ) c -OR 7 ] f

[0083] in:

[0084] a, b and c are 1 to 200;

[0085] d, e and f are 1 to 50;

[0086] Ar is 1,4-substituted phenylene;

[0087] sAr is SO at position 5 3 Me substituted 1,3-substituted phenylene;

[0088] Me is Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl group is C 1 -C 18 Alkyl or C 2 -C 10 Hydroxyalkyl or mixtures thereof;

[0089] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from H or C 1 -C 18 n-alkyl or C 1 -C 18 isoalkyl; and

[0090] R 7 C is a straight chain or branched chain 1 -C 18 Alkyl, or linear or branched C 2 -C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or a C 8 -C 30 Aryl, or C 6 -C 30 Arylalkyl.

[0091] 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.

[0092] Anti-redeposition polymers: Suitable anti-redeposition polymers include polyethylene glycol polymers and / or polyethylene imine polymers.

[0093] 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: 4 -C 25 Alkyl groups, polypropylene, polybutylene, saturated C 1 -C 6 Vinyl esters of monocarboxylic acids, acrylic acid or methacrylic acid 1 -C 6 Alkyl esters, 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.

[0094] Suitable polyethylene glycol polymers are described in WO08 / 007320.

[0095] A suitable polyethylene glycol polymer is Sokalan HP22.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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).

[0101] Other suitable care polymers include amino-silicones, which can provide fabric feel benefits and fabric form retention benefits.

[0102] Enzymes: Suitable enzymes include lipases, proteases, cellulases, amylases, and any combination thereof.

[0103] 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.

[0104] 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 Prefer 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.

[0105] Suitable proteases are described in WO11 / 140316 and WO11 / 072117.

[0106] 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).

[0107] Suitable amylases are described in WO06 / 002643.

[0108] 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.

[0109] 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.

[0110] 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).

[0111] 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).

[0112] 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.

[0113] 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 .

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] Silicate: The composition may include a silicate. The composition may include 0 wt% to 10 wt% silicate, or 0 wt% to 5 wt% silicate. A preferred silicate is sodium silicate, particularly preferred having a Na of 1.0 to 2.8, preferably 1.6 to 2.0. 2 O:SiO2 ratio of sodium silicate.

[0119] Sulphate: A suitable sulphate is sodium sulphate.

[0120] Brighteners: Suitable fluorescent brighteners include: distyrylbiphenyl compounds, such as CBS-X, diaminostilbene disulfonic acid compounds, e.g. DMS pure Xtra and HRH, and pyrazoline compounds, e.g. SN and coumarin compounds, e.g. SWN.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] Suitable hueing agents include phthalocyanine and azo dye conjugates such as described in WO2009 / 069077.

[0128] 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.

[0129] 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.

[0130] Preferred hueing agents may be anthraquinone hueing dyes. A suitable hueing agent is disperse violet 28.

[0131] 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).

[0132] 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.

[0133] 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.

[0134] Silicones: Suitable silicones include polydimethylsiloxanes and amino-silicones. Suitable silicones are described in WO05075616.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] Other suitable detergent ingredients that may be agglomerated include polymers, chelating agents, bleach activators, silicones, and any combination thereof.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] Methods for measuring pH

[0151] 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.

[0152] Embodiments of the present invention

[0153] 1. A free-flowing solid granular laundry detergent composition, wherein the composition

[0154] Include:

[0155] (a) detersive surfactants;

[0156] (b) an iron-based bleach catalyst having the following structure:

[0157] and

[0158] (c) Sulfite-based reducing bleaches.

[0159] 2. The composition according to embodiment 1, wherein the sulfite-based reducing bleach is selected from the group consisting of sulfites, bisulfites, dithionites, metabisulfites, and any combination thereof.

[0160] 3. A composition according to embodiment 2, wherein the sulfite-based reducing bleach is sulfite.

[0161] 4. The composition of embodiment 2, wherein the sulfite-based reducing bleach is bisulfite.

[0162] 5. A composition according to embodiment 2, wherein the sulfite-based reducing bleach is dithionate.

[0163] 6. A composition according to embodiment 2, wherein the sulfite-based reducing bleach is metabisulfite.

[0164] 7. The composition according to any preceding embodiment, wherein the composition has an equilibrium pH greater than 10.0 at a concentration of 1 g / l in deionized water at 20°C.

[0165] 8. The composition according to any one of embodiments 1 to 6, 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.

[0166] 9. A composition according to any preceding embodiment, wherein the composition comprises an anionic detersive surfactant.

[0167] 10. A composition according to embodiment 9, wherein the anionic detersive surfactant is selected from alkyl sulfates and / or alkyl benzene sulfonates.

[0168] 11. A composition according to any preceding embodiment, wherein the composition comprises a non-ionic detersive surfactant.

[0169] 12. A composition according to any preceding embodiment, wherein the composition comprises a dye transfer inhibiting agent.

[0170] 13. A composition according to any preceding embodiment, wherein the composition comprises a hueing dye.

[0171] 14. The composition according to any preceding embodiment, wherein the composition comprises an enzyme.

[0172] 15. A composition according to any preceding embodiment, wherein the composition comprises a soil release polymer.

[0173] Example

[0174] Embodiment 1: Compatibility of iron-based catalysts and reducing bleaching agents

[0175] The following compositions were prepared and tested for stain removal performance.

[0176]

[0177]

[0178] Washing method: The following method demonstrates the ability of the example compositions to remove stains during the washing process. Each composition is added separately to the tank of an oscillating dirt-washing instrument. The volume of each tank is 1L. The washing temperature is set to 27°C. Throughout the process, 7gpg of water is used. The washing solution is stirred for 1 minute (300rpm), and then the fabric is added (two internal repetitions of each stain, and an additional knitted cotton ballast to bring the total fabric weight to 60g). Once the fabric is added, the washing solution is stirred for 17 minutes (208rpm). The washing solution is then drained, and the fabric is subjected to a 5-minute rinse step, then drained and spin-dried. The process washing is repeated three more times, resulting in a total of four external repetitions. After washing, the fabric is washed under simulated solar conditions (UVA intensity (300-400nm) at 16.35 and 33.31w / m 2 The visible intensity (400-700nm) is between 166.0 and 340.0w / m 2 Dry the fabric in between.

[0179] Stain removal effect analysis: The L*a*b* values ​​of the fabrics were analyzed using commercially available image analysis 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.

[0180] %SRI (stain removal effect) = 100*((ΔE b –ΔE a ) / ΔE b )

[0181] ΔE b =√((L c -L b ) 2 +(a c -a b ) 2 +b c -b b ) 2 )

[0182] ΔE a =√((L c -L a ) 2 +(a c -a a ) 2 +b c -b a ) 2 )

[0183] Subscript 'b' indicates the data of stains before washing

[0184] Subscript 'a' indicates the stain data after washing

[0185] Subscript 'c' indicates data for undyed fabric

[0186] Therefore, L*a*b* values ​​were obtained from undyed fabric, dyed fabric before washing and dyed fabric after washing.

[0187]

[0188]

[0189] Dopiaza (a turmeric based stain) was used to evaluate the performance of the FeONIX catalyst. The above examples show that FeONIX is effective in the presence of a reducing bleach.

[0190]

[0191] Inks were used to evaluate the performance of reducing bleach (sulfite). The above examples show that sulfite is effective in the presence of FeONIX bleach.

[0192] Embodiment 2: Performance of iron-based catalysts in the presence of oxygen-based bleaches

[0193]

[0194]

[0195] Washing method: The following method demonstrates the ability of the example compositions to remove stains during the washing process. Each composition is added separately to the tank of an oscillating detergent. The volume of each tank is 1L. The washing temperature is set to 27°C. Throughout the process, 21gpg of water is used. The wash solution is stirred for 1 minute (300rpm) and then the fabric is added (two internal repeats for each stain, and an additional knitted cotton ballast to bring the total fabric weight to 60g). Once the fabric is added, the wash solution is stirred for 17 minutes (208rpm). The wash solution is then drained and the fabric is subjected to a 5-minute rinse step, then drained and spin-dried. The process is repeated three more times for a total of four external repeats. The washed fabric is then dried overnight at 32°C and 80%RH and then analyzed to measure the stains removed from the fabric.

[0196] Stain Removal Effectiveness Analysis: The fabrics were analyzed using commercially available image analysis software and the SRI values ​​were calculated as described in the previous examples.

[0197] Dopiaza Average SRI Standard error Δ, relative to reference Comparative composition 1 66.89 2.76 refer to Comparative composition 2 85.22 1.37 18.33 Comparative composition 4 68.09 3.68 refer to Comparative composition 5 69.20 4.80 1.11

[0198] Dopiaza (turmeric based stain) was used to evaluate the performance of the FeONIX catalyst. The above examples show that FeONIX is ineffective in the presence of oxygen based bleach.

[0199] The dimensions and values ​​disclosed herein are not to 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 following structure: (c) Sulfite-based reducing bleaches.

2. The composition of claim 1, wherein the sulfite-based reducing bleach is selected from the group consisting of sulfites, bisulfites, dithionites, metabisulfites, and any combination thereof.

3. A composition according to claim 2, wherein the sulfite-based reducing bleach is sulfite.

4. The composition of claim 2, wherein the sulfite-based reducing bleach is bisulfite.

5. The composition of claim 2, wherein the sulfite-based reducing bleach is a dithionite salt.

6. The composition of claim 2, wherein the sulfite-based reducing bleach is metabisulfite.

7. A composition according to any preceding claim, wherein the composition has an equilibrium pH greater than 10.0 at a concentration of 1 g / l in deionized water at 20°C.

8. The composition of any one of claims 1 to 6, 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.

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

10. A composition according to claim 9 wherein the anionic detersive surfactant is selected from alkyl sulfates and / or alkyl benzene sulfonates.

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

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 hueing dye.

14. A composition according to any preceding claim, wherein the composition comprises an enzyme.

15. A composition according to any preceding claim, wherein the composition comprises a soil release polymer.

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