EP2899259A1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP2899259A1
EP2899259A1 EP14152209.4A EP14152209A EP2899259A1 EP 2899259 A1 EP2899259 A1 EP 2899259A1 EP 14152209 A EP14152209 A EP 14152209A EP 2899259 A1 EP2899259 A1 EP 2899259A1
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EP
European Patent Office
Prior art keywords
alkyl
process according
surfactant
detergent
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP14152209.4A
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German (de)
English (en)
Inventor
Hossam Hassan Tantawy
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP14152209.4A priority Critical patent/EP2899259A1/fr
Priority to PCT/US2015/010614 priority patent/WO2015112342A1/fr
Publication of EP2899259A1 publication Critical patent/EP2899259A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention is directed to compositions comprising optical brightener and polymer and to methods of making granular detergent compositions containing optical brighteners and polymer.
  • optical brightener is used in combination with an amphiphilic graft copolymer (AGP), optimal performance of the brightener results.
  • AGP amphiphilic graft copolymer
  • the present invention addresses the aforementioned needs by providing a detergent composition comprising from 0.0001 to 10 wt% of an optical brightener having a ClogP from 1 to 50 and from 0.05 to 10 wt% of an amphiphilic graft copolymer.
  • the invention also provides a method of making a granular detergent composition comprising the steps of: a) forming an aqueous detergent slurry; b) spray drying said aqueous detergent slurry to form a plurality of spray-dried detergent particles; c) forming an emulsion comprising a surfactant, an optical brightener having ClogP from 1 to 50 and an amphiphilic graft co-polymer; and d) adding the emulsion from step c) to at least a portion of said plurality of spray-dried detergent particles.
  • compositions or component may include additional ingredients, but only if the additional ingredients do not materially alter the basic and novel characteristics of the claimed compositions or methods.
  • Granular laundry detergents may be manufactured using a spray drying process.
  • the spray drying process typically includes spraying an aqueous slurry comprising detergent ingredients into a spray-drying tower through which hot air flows. As it falls through the tower, the aqueous slurry forms droplets, the hot air causes water to evaporate from the droplets, and a plurality of spray-dried granules is formed.
  • the resulting granules may form the finished granular detergent composition.
  • the resulting granules may be further processed (such as via agglomeration) and/or further components (such as detergent adjuncts) may be added thereto.
  • the process of the present invention can be batch, continuous, or semi-continuous.
  • optical brightener in combination with the amphiphilic graft polymer enables better dispersion of the optical brightener as the detergent composition contacts the wash water, leading to increased performance of the optical brightener.
  • AGP(s) of use in the present invention are obtainable by grafting a polyalkylene oxide of number average molecular weight from about 2,000 to about 100,000 with vinyl acetate, which may be partially saponified, in a weight ratio of polyalkylene oxide to vinyl acetate of about 1:0.2 to about 1:10.
  • the vinyl acetate may, for example, be saponified to an extent of up to 15%.
  • the polyalkylene oxide may contain units of ethylene oxide, propylene oxide and/or butylene oxide. Selected embodiments comprise ethylene oxide.
  • the polyalkylene oxide has a number average molecular weight of from about 4,000 to about 50,000, and the weight ratio of polyalkylene oxide to vinyl acetate is from about 1:0.5 to about 1:6.
  • a material within this definition based on polyethylene oxide of molecular weight 6,000 (equivalent to 136 ethylene oxide units), containing approximately 3 parts by weight of vinyl acetate units per 1 part by weight of polyethylene oxide, and having itself a molecular weight of about 24,000, is commercially available from BASF as SokalanTM HP22.
  • HP22 is a preferred AGP as it provides improved grease stain removal from fabrics during the wash.
  • AGP(s) of use in the present invention are described in detail in PCT Patent Application No. WO 2007/138054 . They may be present in the granular detergent compositions of the present invention at weight percentages from about 0 to about 5%, from about 0% to about 4%, or from about 0.5% to about 2%. In some embodiments, the AGP(s) is present at greater than about 1.5%. The AGP(s) are found to provide excellent hydrophobic soil suspension even in the presence of cationic coacervating polymers.
  • the AGP(s) are based on water-soluble polyalkylene oxides as a graft base and side chains formed by polymerization of a vinyl ester component. These polymers having an average of less than or equal to one graft site per 50 alkylene oxide units and mean molar masses (M w ) of from about 3000 to about 100,000.
  • the optical brightener typically has a ClogP of 1 to 50 (herein, high ClogP), or 2 to 50, or 2.5 to 50, or 3 to 50 or up to 40 or 30 or 20 or up to 10.
  • ClogP is calculated using Advanced Chemistry Development Software V11.02 ( ⁇ 1994-2012 ACD/Labs), Advanced Chemistry Development, Inc., 8 King Street East, Suite 107, Toronto, Ontario, Canada M5C 1B5.
  • the optical brightener preferably has an extinction co-efficient at the maximum absorbance between 400 and 750nm of less than 1000L/mol cm.
  • Preferred optical brighteners include coumarinic and benzoxazole brighteners or mixtures thereof.
  • Coumarinic optical brighteners are particularly preferred.
  • a preferred brightener is selected from coumarinic compounds of Formula I wherein R 3 is selected from the group consisting of H, C1-C4 alkyl, and C6-C10 aromatic or heteroaromatic groups which may be substituted with -F, -Cl, -Br, phenyl and C1-C4 alkyl;
  • R 4 is selected from the group consisting of H, C1-C4 alkyl optionally substituted by OH or (OCH 2 CHR 9 ) x OH wherein each R 9 is independently selected from H, methyl, and ethyl and x is 1 to 20;
  • R 5 is H, R 6 and R 8 are selected from H and C2-C4 alkylene that combine with one of more of R 7 and R 7' to form a heterocyclic ring;
  • R 7 and R 7' are selected
  • Preferred optical brightener for use in the present invention may be selected from compounds of Formula I wherein R 3 is selected from the group consisting of H, methyl, phenyl optionally substituted with -Cl or C1-C4 alkyl, preferably methyl, triazole optionally substituted with phenyl or C1 - C4 alkyl, and pyrazole optionally substituted with phenyl; R 4 is selected from the group consisting of H, methyl and ethyl optionally substituted by OH or (OCH 2 CHR 9 ) x OH wherein each R 9 is independently selected from H and methyl, and x is 1 to 10; R 5 ,R 6 and R 8 are H; R 7 and R 7' are selected from the group consisting of H and organic groups that have mass less than 350 Daltons, wherein R 7 and R 7' may combine with one another to form a heterocyclic ring, and mixtures thereof.
  • a preferred optical brightener for use in the present invention may be selected from compounds of Formula I wherein R 3 is selected from the group consisting of H, methyl, and phenyl; R 4 is selected from the group consisting of H and methyl; R 5 ,R 6 and R 8 are H; R 7 and R 7' are selected from the group consisting of H, C1-C12 branched or unbranched alkyl, and (CH 2 CHR 9 O) x H where each R 9 is independently selected from H, methyl, and ethyl and x is 1 to 20, and mixtures thereof.
  • a preferred optical brightener for use in the present invention may be selected from benzoxazole compounds of Formula II wherein the index y is 1 or 2 and each R 10 is independently selected from the group consisting of H, -F, -Cl, -Br, C1-C10 alkyl optionally substituted with halo, C6-C10 aryl, C7-C10 alkaryl, -G z -N(R 12 ) 2 where z is 0 or 1 and G is selected from the group consisting of C(O) and SO2 and each R 12 is independently selected from H, C1-C4 alkyl and (CH 2 CHR 9 O) x H, and C1-C4 alkyl optionally substituted by OH or (OCH 2 CHR 9 ) x OH, wherein each R 9 is independently selected from H, methyl, and ethyl and x is 1 to 20; R 11 is selected from the group consisting of aromatic and heteroaromatic organic groups having no carboxylic acid or
  • Preferred optical brightener for use in the present invention may be selected from compounds of Formula III wherein each index y is independently selected from 1 or 2 and each R 10 is independently selected from the group consisting of H, -F, -Cl, -Br, C1-C10 alkyl optionally substituted with halo, C6-C10 aryl, C7-C10 alkaryl, -G z N(R 12 ) 2 where z is 0 or 1 and G is selected from the group consisting of C(O) and SO2 and each R 12 is independently selected from H, C1-C4 alkyl and (CH 2 CHR 9 O) x H, and C1-C4 alkyl optionally substituted by OH or (OCH 2 CHR 9 ) x OH, wherein each R 9 is independently selected from H, methyl, and ethyl and x is 1 to 20; Q is a divalent moiety weighing less than 400 Daltons comprising an aromatic or heteroaromatic group and preferably having no
  • Suitable Q groups in Formula III include, but are not limited to, 1,4-naphthalene, 1,7-naphthalene, 4,4-terphenylene, 2,7-dihydro[9,10]phenanthrene, 2,5-thiophene, 4-methyl-2,5-oxazole, 2,5-1,3,4-thiadiazole, 4,4'-(1,2,3-triazol-2-yl)phenyl, 2,6-thieno[3,2-b]benzothiophene, 2,4'-(1,3,4-oxadiazol-5-yl)phenyl, and mixtures thereof.
  • the optical brightener is present in the composition in an amount from 1ppb to 10 wt% of the composition.
  • the composition may be a pre-treatmenet composition for applying directly to an oily stain prior to an aqueous wash or rinse step or it may be provided by combining a detergent composition with water to form a wash liquor.
  • concentration may vary widely depending on the form of application.
  • the optical brightener may be present in amounts from 1ppb to 50ppm in a wash liquor/solution, preferably from 100ppb or 500ppb to 35ppm.
  • a pre-treat composition or detergent compostion for dilution more usually in an amount from 0.00001 to 10 wt%, or from 0.0001 or 0.01 or even from 0.05 to 5 or 2 wt% of the pre-treat or detergent composition.
  • the optical brightener may be incorporated into the detergent composition by first forming a pre-mix comprising the optical brightener, for example where the pre-mix comprises a particle or concentrated liquid for incorporation into the composition, it may be preferred that the optical brightener is present at a level of from 0.001 or even 0.01 to 10 wt% of the pre-mix.
  • Examples of preferred brighteners are shown in Table 1.
  • Table 1 Optical brighteners No. Formula Example 1 7-(4-methyl-1-oxido-5-pentyl-2H-1,2,3-triazol-2-yl)-3-phenyl-2H-1-benzopyran-2-one
  • Example 2 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one
  • Example 3 N-[4-[(4-methyl-2-oxo-2H-1-benzopyran-7-yl)amino]-6-(4-morpholinyl)-1,3,5-triazin-2-yl]-N'-(4-nitrophenyl)urea
  • Example 4 2,2'-(2,5-thiophenediyl)bis[5-(1-methyl-1-phenylethyl)benzoxazole
  • Example 5 2,2'-(2,5-thiophenediyl)bis[5-(1,1,3,3-tetramethylbutyl)benzo
  • Any suitable detersive surfactant is of use in the aqueous slurry.
  • Suitable detersive surfactants include, but are not limited to: anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and any mixtures thereof.
  • Preferred surfactants include anionic surfactants, cationic surfactants, non-ionic surfactants and any mixtures thereof.
  • Suitable anionic surfactants can include alkyl benzene sulphonate.
  • the anionic detersive surfactant comprises at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, or even at least 95 wt%, by weight of the anionic detersive surfactant, of alkyl benzene sulphonate.
  • the alkyl benzene sulphonate is preferably a linear or branched, substituted or unsubstituted, C 8-18 alkyl benzene sulphonate. This is the optimal level of the C 8-18 alkyl benzene sulphonate to provide a good cleaning performance.
  • the C 8-18 alkyl benzene sulphonate can be a modified alkylbenzene sulphonate (MLAS) as described in more detail in WO 99/05243 , WO 99/05242 , WO 99/05244 , WO 99/05082 , WO 99/05084 , WO 99/05241 , WO 99/07656 , WO 00/23549 , and WO 00/23548 .
  • Highly preferred C 8-18 alkyl benzene sulphonates are linear C 10-13 alkylbenzene sulphonates.
  • linear C 10-13 alkylbenzene sulphonates that are obtainable by sulphonating commercially available linear alkyl benzenes (LAB);
  • suitable LAB include low 2-phenyl LAB, such as those supplied by Sasol under the trade name Isochem ® or those supplied by Petresa under the trade name Petrelab ® .
  • Other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the trade name Hyblene ® .
  • the anionic detersive surfactant may preferably comprise other anionic detersive surfactants.
  • a suitable anionic detersive surfactant is a non-alkoxylated anionic detersive surfactant.
  • the non-alkoxylated anionic detersive surfactant can be an alkyl sulphate, an alkyl phosphate, an alkyl phosphonate, an alkyl carboxylate or any mixture thereof.
  • the non-alkoxylated anionic surfactant can be selected from the group consisting of; C 10 -C 20 primary, branched-chain, linear-chain and random-chain alkyl sulphates (AS), typically having the following formula (I): CH 3 (CH 2 ) x CH 2 -OSO 3 - M + wherein, M is hydrogen or a cation which provides charge neutrality, preferred cations are sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9; C 10 -C 18 secondary (2,3) alkyl sulphates, typically having the following formulae: wherein, M is hydrogen or a cation which provides charge neutrality, preferred cations include sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9, y is an integer of at least 8, preferably at least 9; C 10 -C 18 alkyl carboxylates; mid-chain branched alkyl sulphates as described in more detail in US
  • anionic detersive surfactant is an alkoxylated anionic detersive surfactant.
  • the presence of an alkoxylated anionic detersive surfactant in the spray-dried powder provides good greasy soil cleaning performance, gives a good sudsing profile, and improves the hardness tolerance of the anionic detersive surfactant system.
  • the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted C 12-18 alkyl alkoxylated sulphate having an average degree of alkoxylation of from 0.5 to 30, preferably from 0.5 to 10, more preferably from 0.5 to 3.
  • the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted C 12-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, more preferably from 0.5 to 3.
  • the alkoxylated anionic detersive surfactant is a linear unsubstituted C 12-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 7, more preferably from 0.5 to 3.
  • the alkoxylated anionic detersive surfactant when present with an alkyl benzene sulphonate may also increase the activity of the alkyl benzene sulphonate by making the alkyl benzene sulphonate less likely to precipitate out of solution in the presence of free calcium cations.
  • the weight ratio of the alkyl benzene sulphonate to the alkoxylated anionic detersive surfactant is in the range of from 1:1 to less than 5:1, or to less than 3:1, or to less than 1.7:1, or even less than 1.5:1. This ratio gives optimal whiteness maintenance performance combined with a good hardness tolerance profile and a good sudsing profile.
  • the weight ratio of the alkyl benzene sulphonate to the alkoxylated anionic detersive surfactant is greater than 5:1, or greater than 6:1, or greater than 7:1, or even greater than 10:1. This ratio gives optimal greasy soil cleaning performance combined with a good hardness tolerance profile, and a good sudsing profile.
  • Suitable alkoxylated anionic detersive surfactants are: Texapan LESTTM by Cognis; Cosmacol AESTM by Sasol; BES151TM by Stephan; Empicol ESC70/UTM; and mixtures thereof.
  • the anionic detersive surfactant comprises from 0% to 10%, preferably to 8%, or to 6%, or to 4%, or to 2%, or even to 1%, by weight of the anionic detersive surfactant, of unsaturated anionic detersive surfactants such as alpha-olefin sulphonate.
  • the anionic detersive surfactant is essentially free of unsaturated anionic detersive surfactants such as alpha-olefin sulphonate.
  • By “essentially free of” it is typically meant “comprises no deliberately added”. Without wishing to be bound by theory, it is believed that these levels of unsaturated anionic detersive surfactants such as alpha-olefin sulphonate ensure that the anionic detersive surfactant is bleach compatible.
  • the anionic detersive surfactant comprises from 0% to 10%, preferably to 8%, or to 6%, or to 4%, or to 2%, or even to 1%, by weight of alkyl sulphate.
  • the anionic detersive surfactant is essentially free of alkyl sulphate. Without wishing to be bound by theory, it is believed that these levels of alkyl sulphate ensure that the anionic detersive surfactant is hardness tolerant.
  • the non-ionic detersive surfactant could be an alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • the non-ionic detersive surfactant is a linear or branched, substituted or unsubstituted C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, more preferably from 3 to 7.
  • Suitable alkalinity source is of use in the aqueous slurry.
  • Suitable alkalinity sources include, but are not limited to being selected from the group of: carbonate salt; silicate salt; sodium hydroxide; and mixtures thereof.
  • Exemplary alkalinity sources may be selected from the group of: sodium carbonate; sodium silicate; and mixtures thereof.
  • the additional detergent ingredient may include a builder.
  • Any suitable builder may be of use in the aqueous slurry.
  • Suitable builders include, but are not limited to those selected from the group of: zeolite builder; phosphate builder; and mixtures thereof.
  • Non-limiting examples of useful zeolite builders include: zeolite A; zeolite X; zeolite P; zeolite MAP; and combinations thereof.
  • Sodium tripolyphosphate is a non-limiting example of a useful phosphate builder.
  • the zeolite builder(s) may be present at from about 1 to about 20 % by weight of the detergent composition. It may also be especially preferred for the granular detergent composition to comprise low levels, or even be essentially free, of builder.
  • the granular detergent composition is essentially free of zeolite, preferably has no zeolite.
  • the granular detergent composition is essentially free of phosphate, preferably has no phosphate.
  • the additional detergent ingredient may include a polymer.
  • Any suitable polymer may be of use in the aqueous slurry. Suitable polymers include, but are not limited to: polymeric carboxylate; polyester soil release agent; cellulosic polymer; and mixtures thereof.
  • One preferred polymeric material is a polymeric carboxylate, such as a co-polymer of maleic acid and acrylic acid.
  • other polymers may also be suitable, such as polyamines (including the ethoxylated variants thereof), polyethylene glycol and polyesters.
  • Polymeric soil suspending aids and polymeric soil release agents are also particularly suitable.
  • cellulosic polymer such as cellulosic polymer selected from the group of: alkyl alkoxy cellulose, preferably methyl hydroxyethyl cellulose (MHEC); alkyl cellulose, preferably methyl cellulose (MC); carboxy alkyl cellulose, preferably carboxymethylcellulose (CMC); and mixtures thereof.
  • MHEC methyl hydroxyethyl cellulose
  • MC methyl cellulose
  • CMC carboxymethylcellulose
  • Polymers may be present at from about 0.5 to about 20% or from about 1 to about 10% by weight of the detergent composition.
  • Suitable detergent ingredients may be selected from the group of: chelants such as ethylene diamine disuccinic acid (EDDS); hydroxyethylene diphosphonic acid (HEDP); starch; sodium sulphate; carboxylic acids such as citric acid or salts thereof such as citrate; suds suppressor; fluorescent whitening agent; hueing agent; flocculating agent such as polyethylene oxide; and mixtures thereof.
  • chelants such as ethylene diamine disuccinic acid (EDDS); hydroxyethylene diphosphonic acid (HEDP); starch; sodium sulphate; carboxylic acids such as citric acid or salts thereof such as citrate; suds suppressor; fluorescent whitening agent; hueing agent; flocculating agent such as polyethylene oxide; and mixtures thereof.
  • the present detergent comprises masking agents and/or whiteners (e.g. Titanium dioxide), they may be present at less than about 1 wt% or less.
  • the emulsion comprises a surfactant continuous phase and an amphiphilic graft copolymer (AGP) discrete phase.
  • AGP amphiphilic graft copolymer
  • the surfactant and the AGP are immiscible with other.
  • the surfactant is water-soluble and independently the AGP is water-soluble.
  • the surfactant and the AGP are water-soluble.
  • the graft co-polymer has a viscosity of up to 4Pa.s at 55°C, or even up to 3Pa.s. The viscosity is typically measured using a rheometer at a shear of 100s -1 and a temperature of 70°C. Those skilled in the art will recognize suitable apparatus in order to measure the viscosity.
  • An exemplary method is to measure the viscosity at a shear rate of 100s -1 at temperature of 70°C, using a TA AR 2000ex, controlled stress rheometer, using a TA Instruments Peltier Concentric Cylinder Conical DIN System, hard anodized Aluminium cup and rotor, having a rotor radius of 14mm, a rotor height of 42mm, a cup radius of 15mm, and a sample volume of 19.6ml.
  • this viscosity is preferred as it allows more efficient spraying of the emulsion on the spray-dried detergent particles.
  • the ratio of surfactant to AGP can be from 1:2 to 2:1.
  • AGP(s) amphiphilic graft copolymer(s)
  • spray-dried powder has a consumer undesirable yellow hue.
  • the yellowing can be especially problematic in detergent matrices having high alkalinity and/or that are processed under high temperature conditions.
  • discoloration of the granules results from the occurrence of one or more chemical reactions with the AGP(s) as it is subjected to the conditions in the tower. Such reactions may include:
  • the surfactant can be selected from non-ionic, cationic, anionic, zwitterionic surfactants and mixtures thereof.
  • the surfactant may be a non-ionic surfactant, an anionic surfactant or a mixture thereof.
  • the surfactant may be a non-ionic surfactant, or even an alkoxylated non-ionic surfactant.
  • the surfactant is anhydrous. This has the benefit of limiting the amount of water that is transferred onto the spray-dried detergent particles. It is most preferred to use a non-ionic anhydrous surfactant as this as a lower viscosity as compared to other anhydrous surfactants.
  • the non-ionic surfactant for use in the emulsion could be an alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • the non-ionic surfactant is a linear or branched, substituted or unsubstituted C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, more preferably from 3 to 7.
  • Suitable non-ionic surfactants include alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • Preferred non-ionic alkyl alkoxylated alcohols include C 8-18 alkyl alkoxylated alcohol, preferably a C 8-18 alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7.
  • the alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
  • Suitable non-ionic surfactants can be selected from the group consisting of: C 8 -C 18 alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C 6 -C 12 alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C 14 -C 22 mid-chain branched alcohols; C 14 -C 22 mid-chain branched alkyl alkoxylates, preferably having an average degree of alkoxylation of from 1 to 30; alkylpolysaccharides, preferably alkylpolyglycosides; polyhydroxy fatty acid
  • Anionic surfactants can include sulphate and sulphonate surfactants.
  • Preferred sulphonate surfactants include alkyl benzene sulphonate, preferably C 10-13 alkyl benzene sulphonate.
  • Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • a suitable anionic surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable.
  • Preferred sulphate surfactants include alkyl sulphate, preferably C 8-18 alkyl sulphate, or predominantly C 12 alkyl sulphate.
  • alkyl alkoxylated sulphate preferably alkyl ethoxylated sulphate, preferably a C 8-18 alkyl alkoxylated sulphate, preferably a C 8-18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C 8-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 7, more preferably from 0.5 to 5 and most preferably from 0.5 to 3.
  • the alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted.
  • Suitable organic anionic surfactants include alkyl aryl sulphonates, for example sodium dodecyl benzene sulphonate, long chain (fatty) alcohol sulphates, olefin sulphates and sulphonates, sulphated monoglycerides, sulphated esters, sulphonated or sulphated ethoxylate alcohols, sulphosuccinates, alkane sulphonates, alkali metal soaps of higher fatty acids, phosphate esters, alkyl isethionates, alkyl taurates and/or alkyl sarcosinates.
  • alkyl aryl sulphonates for example sodium dodecyl benzene sulphonate, long chain (fatty) alcohol sulphates, olefin sulphates and sulphonates, sulphated monoglycerides, sulphated esters, sulphonated or sulphated e
  • Suitable cationic surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
  • Preferred cationic surfactants are quaternary ammonium compounds having the general formula: (R)(R 1 )(R 2 )(R 3 )N + X - wherein, R is a linear or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R 1 and R 2 are independently selected from methyl or ethyl moieties, R 3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include: halides, preferably chloride; sulphate; and sulphonate.
  • Preferred cationic detersive surfactants are mono-C 6-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly preferred cationic detersive surfactants are mono-C 8-10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C 10-12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-C 10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
  • a cationic surfactant can for example be an alkylamine salt, a quaternary ammonium salt, a sulphonium salt or a phosphonium salt.
  • a zwitterionic (amphoteric) surfactant can for example be an imidazoline compound, an alkylaminoacid salt or a betaine.
  • the detergent composition is suitable for any laundry detergent application, for example: laundry, including automatic washing machine laundering and hand laundering, and even bleach and laundry additives.
  • the detergent composition can be a fully formulated detergent product, such as a fully formulated laundry detergent product, or it can be combined with other particles to form a fully formulated detergent product, such as a fully formulated laundry detergent product.
  • the detergent composition is a granular detergent composition it may be combined with other particles such as: enzyme particles; perfume particles including agglomerates or extrudates of perfume microcapsules, and perfume encapsulates such as starch encapsulated perfume accord particles; surfactant particles, such as non-ionic detersive surfactant particles including agglomerates or extrudates, anionic detersive surfactant particles including agglomerates and extrudates, and cationic detersive surfactant particles including agglomerates and extrudates; polymer particles including soil release polymer particles, cellulosic polymer particles; buffer particles including carbonate salt and/or silicate salt particles, preferably a particle comprising carbonate salt and silicate salt such as a sodium carbonate and sodium silicate co-particle,
  • the granular detergent composotion may also be especially preferred for the granular detergent composotion to comprise low levels, or even be essentially free, of builder. By essentially free of it is typically meant herein to mean: “comprises no deliberately added”. In a preferred embodiment, the granular detergent composition comprises no builder.
  • the whiteness of the granular detergent composition can be measured using a HunterLab Color difference meter and following appropriate operating procedure.
  • Various models of the HunterLab Color difference meter can be used, such as the HunterLab LabScan XE or HunterLab Model D25. Care is taken to make sure that the powder sample is free of lumps and is representative of the overall particle size. The readings are taken at ambient temperature.
  • a HunterLab color difference meter is used to characterize color of a sample into three different parameters according to the Hunter L, a, b color scale. In this scale, the differences between points plotted in a color space correspond to visual differences between the colors plotted.
  • the Hunter L, a, b color scale is organized in cube form. The L axis of the cube runs from top to bottom. The maximum for L is 100, which would be a perfect reflecting diffuser. The minimum for L would be zero, which would be black.
  • the a and b axes of the cube have no specific numerical limits. Positive a is red. Negative a is green. Positive b is yellow. Negative b is blue.
  • the "L-3b" (L minus 3b) value signifies the whiteness of the sample.
  • the whiteness of a blown powder according to the present invention is at least about 73.5.
  • the granular detergent composition according to the present invention may have a bulk density of from about 250 to about 550 grams per liter, or from about 300 to about 450 grams per liter.
  • the granular detergent composition may have a mean particle granule size of from about 300 to about 550 microns, or from about 350 to about 450 microns.
  • a granular laundry detergent composition according to the present invention is prepared.
  • An aqueous alkaline slurry composed of sodium sulphate, sodium carbonate, water, acrylate/maleate co-polymer and miscellaneous ingredients is prepared at 80 °C in a crutcher making vessel.
  • the aqueous slurry is essentially free from zeolite builder and essentially free from phosphate builder.
  • Alkyl benzene sulphonic acid (HLAS) and sodium hydroxide are added to the aqueous slurry and the slurry is pumped through a standard spray system pressure nozzle and atomized into a counter current spray drying tower at an air inlet temperature of 275 °C.
  • the atomized slurry is dried to produce a solid mixture, which is then cooled and sieved to remove oversize material (>1.8mm) to form a spray-dried powder.
  • composition of the spray-dried powder is given Table 1.
  • Table 1 Component %w/w Spray Dried Powder Sodium silicate salt 10.0 C 8 -C 24 alkyl benzene sulphonate 15.1 Acrylate/maleate copolymer 4.0 Hydroxyethane di(methylene phosphonic acid) 0.7 Sodium carbonate 11.9 Sodium sulphate 53.7 Water 2.5 Miscellaneous, such as magnesium sulphate, and one or more stabilizers 2.1 Total Parts 100.00
  • Table 2 Component %w/w granular laundry detergent composition Spray-dried powder (described above in table 1) 59.38 91.6wt% active linear alkyl benzene sulphonate flake supplied by Stepan under the tradename Nacconol 90G ® 0.22 Citric acid 5.00 Sodium percarbonate (having from 12% to 15% active AvOx) 14.70 Photobleach particle 0.01 Lipase (11.00mg active/g) 0.70 Amylase (21.55mg active
  • the granular laundry detergent composition of Table 2 is prepared by dry-mixing all of the above components (all except the AE7, Sokalan HP22 polymer and optical brightener, 7-(Diethylamino)-4-methyl-2H-chromen-2-one) in a continuous rotary mixer (drum diameter 0.6 meters, drum length 1.8 meters, 28 revolutions per min). The total mass flow rate of the powder feeds into the continuous rotary mixer set at 2913 kg/hr. A mixture of AE7 in liquid form and Sokalan HP22 polymer and 7-(Diethylamino)-4-methyl-2H-chromen-2-one in liquid form is sprayed on the particles as they pass through the continuous rotary mixer.
  • the mass flow rate of the liquid mixture is set to 88.9 kg/hr according to formulation in table 2.
  • the liquid mixture is atomized into droplets by air assisted nozzles operating at a air supply pressure of 5.2 bar gauge prior to liquid mixture addition into the continuous rotary mixer.
  • a granular detergent composition (Granular detergent A) is prepared where the liquid mixture is first emulsified (AE7 continuous phase) by passing through a high shear dynamic mixer (IKA Dispax-Reactor®; Model Size: DR2000/ Mixer Speed 4000 rpm) prior to atomizing and adding to powder.
  • a high shear dynamic mixer IKA Dispax-Reactor®; Model Size: DR2000/ Mixer Speed 4000 rpm

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017216521A1 (fr) * 2016-06-15 2017-12-21 Reckitt Benckiser Vanish B.V. Composition comprenant un azurant optique à base de benzonitrile ou benzoxazole ou benzopyrazol

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3546554A1 (fr) * 2018-03-28 2019-10-02 The Procter & Gamble Company Procédé de séchage par atomisation

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0044995A1 (fr) * 1980-07-23 1982-02-03 CASSELLA Aktiengesellschaft Dispersion d'azurants optiques contenant des polymères greffés
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
EP0358474A2 (fr) * 1988-09-07 1990-03-14 Unilever Plc Compositions détergentes
WO1992006162A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
WO1993019146A1 (fr) 1992-03-16 1993-09-30 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
WO1993019038A1 (fr) 1992-03-26 1993-09-30 The Procter & Gamble Company Procede d'abaissement des niveaux de contaminants acides gras dans les tensioactifs a base d'amides d'acides gras polyhydroxy
WO1994009099A1 (fr) 1992-10-13 1994-04-28 The Procter & Gamble Company Compositions fluides contenant des amides d'acides gras polyhydroxy
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
EP0686691A1 (fr) * 1994-06-10 1995-12-13 The Procter & Gamble Company Emulsions aqueuses avec des agents de blanchiment
WO1999005084A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procede de preparation de tensioactifs alkylbenzenesulfonate a partir d'alcools et produits contenant lesdits tensioactifs
WO1999005243A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Compositions detergentes contenant des melanges de tensio-actifs a cristallinite disloquee
WO1999005244A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999005082A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procedes ameliores de preparation de tensioactifs alkylbenzenesulfonate et produits contenant lesdits tensioactifs
WO1999005242A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
WO1999005241A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Produits de nettoyage comportant des tensioactifs alkylarylsulfonate ameliores prepares a l'aide d'olefines de vinylidene et procedes de preparation desdits produits
WO1999007656A2 (fr) 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
WO2000023548A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2000023549A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
WO2007138054A1 (fr) 2006-05-31 2007-12-06 The Procter & Gamble Company Compositions de nettoyage comprenant des polymères greffés amphiphiles à base d'oxydes de polyalkylène et des esters vinyliques
US20110152160A1 (en) * 2009-12-18 2011-06-23 Rohan Govind Murkunde Method of making granular detergent compositions comprising amphiphilic graft copolymers
US20120304402A1 (en) * 2011-06-03 2012-12-06 Gregory Scot Miracle Laundry care compositions containing dyes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2832844A1 (fr) * 2013-07-30 2015-02-04 The Procter & Gamble Company Procédé de fabrication de compositions détergentes comprenant des polymères

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0044995A1 (fr) * 1980-07-23 1982-02-03 CASSELLA Aktiengesellschaft Dispersion d'azurants optiques contenant des polymères greffés
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
EP0358474A2 (fr) * 1988-09-07 1990-03-14 Unilever Plc Compositions détergentes
WO1992006162A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
WO1993019146A1 (fr) 1992-03-16 1993-09-30 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
WO1993019038A1 (fr) 1992-03-26 1993-09-30 The Procter & Gamble Company Procede d'abaissement des niveaux de contaminants acides gras dans les tensioactifs a base d'amides d'acides gras polyhydroxy
WO1994009099A1 (fr) 1992-10-13 1994-04-28 The Procter & Gamble Company Compositions fluides contenant des amides d'acides gras polyhydroxy
EP0686691A1 (fr) * 1994-06-10 1995-12-13 The Procter & Gamble Company Emulsions aqueuses avec des agents de blanchiment
EP0686691B1 (fr) 1994-06-10 2001-08-08 The Procter & Gamble Company Emulsions aqueuses avec des azurants optiques
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6153577A (en) 1996-11-26 2000-11-28 The Procter & Gamble Company Polyoxyalkylene surfactants
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
WO1999005242A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
WO1999005243A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Compositions detergentes contenant des melanges de tensio-actifs a cristallinite disloquee
WO1999005241A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Produits de nettoyage comportant des tensioactifs alkylarylsulfonate ameliores prepares a l'aide d'olefines de vinylidene et procedes de preparation desdits produits
WO1999005084A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procede de preparation de tensioactifs alkylbenzenesulfonate a partir d'alcools et produits contenant lesdits tensioactifs
WO1999005082A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procedes ameliores de preparation de tensioactifs alkylbenzenesulfonate et produits contenant lesdits tensioactifs
WO1999005244A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
WO1999007656A2 (fr) 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
WO2000023549A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2000023548A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
WO2007138054A1 (fr) 2006-05-31 2007-12-06 The Procter & Gamble Company Compositions de nettoyage comprenant des polymères greffés amphiphiles à base d'oxydes de polyalkylène et des esters vinyliques
US20110152160A1 (en) * 2009-12-18 2011-06-23 Rohan Govind Murkunde Method of making granular detergent compositions comprising amphiphilic graft copolymers
US20120304402A1 (en) * 2011-06-03 2012-12-06 Gregory Scot Miracle Laundry care compositions containing dyes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017216521A1 (fr) * 2016-06-15 2017-12-21 Reckitt Benckiser Vanish B.V. Composition comprenant un azurant optique à base de benzonitrile ou benzoxazole ou benzopyrazol
GB2551487A (en) * 2016-06-15 2017-12-27 Reckitt Benckiser Vanish Bv Composition
CN109415661A (zh) * 2016-06-15 2019-03-01 雷克特本克斯尔万尼施公司 包含苯甲腈或苯并噁唑或苯并吡唑增白剂的组合物

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