WO2019144372A1 - Granulés détergents ayant une teneur en tensioactif anionique élevée - Google Patents

Granulés détergents ayant une teneur en tensioactif anionique élevée Download PDF

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Publication number
WO2019144372A1
WO2019144372A1 PCT/CN2018/074284 CN2018074284W WO2019144372A1 WO 2019144372 A1 WO2019144372 A1 WO 2019144372A1 CN 2018074284 W CN2018074284 W CN 2018074284W WO 2019144372 A1 WO2019144372 A1 WO 2019144372A1
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Prior art keywords
detergent granule
detergent
core
surfactant
silica
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PCT/CN2018/074284
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English (en)
Inventor
Dan Xu
Rui Shen
Xiao Tian
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP18902635.4A priority Critical patent/EP3743504B1/fr
Priority to PCT/CN2018/074284 priority patent/WO2019144372A1/fr
Priority to CN201880083216.5A priority patent/CN111511890B/zh
Publication of WO2019144372A1 publication Critical patent/WO2019144372A1/fr

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • This invention relates to detergent granules with a relatively high total anionic surfactant content for use in granular detergent compositions.
  • Granular detergent compositions of today are trending more and more toward high compaction, which enables a myriad of benefits including superior cleaning, environmental sustainability, convenience and efficiency.
  • Such high compaction granular detergent compositions are formed by detergent granules with high concentrations of cleaning actives or surfactants, especially those with high concentrations of anionic surfactants and blends thereof.
  • the desired surfactant concentration may be as high as 40%to 90%, preferably 50%to 80%, by total weight of the detergent granules.
  • the surfactants are mainly anionic surfactants.
  • anionic surfactants are the dominant components in the detergent granules
  • the physical strength of the detergent granules is significantly worsened in comparison with detergent granules with lower anionic surfactant contents.
  • the granule surface is significantly stickier. Both factors contribute to poor flowability of the resulting granules, which in turn leads to challenges in bulk-handling of such detergent granules during the manufacturing process.
  • the present invention discovered, surprisingly and unexpectedly, that the addition of a non-quaternized alkoxylated polyethyleneimine into detergent granules of high anionic surfactant concentrations and the formation of a silica coating layer thereover can significantly increase the flowability of such detergent granules.
  • the present invention relates to a detergent granule that is characterized by a total anionic surfactant content ranging from about 40%to about 90%by weight.
  • a detergent granule contains:
  • a core that contains: (a) one or more anionic surfactants; and (b) a non-quaternized alkoxylated polyethyleneimine having a polyalkyleneimine core with one or more alkoxy side chains bonded to at least one nitrogen atom in the polyalkyleneimine core; anda coating layer over the core, while such coating layer contains silica.
  • the present invention relates to a detergent granule containing:
  • a core that contains: (i) from about 40%to about 9%, by total weight of the detergent granule, of a C 12 -C 14 linear alkylethoxylated sulfate (AES) surfactant having a weight average degree of ethoxylation of from about 0.5 to about 1; (ii) from about 10%to about 50%, by total weight of the detergent granule, of a C 12 -C 14 linear alkyl benzene sulphonate (LAS) surfactant; (iii) from about 1%to about 10%, by total weight of the detergent granule, of a non-quaternized alkoxylated polyethyleneimine having an empirical formula (I) of (PEI) x- (EO) y-R 3 , while x is the average number-average molecular weight of the polyalkyleneimine core (MWPEI) of the alkoxylated polyalkyleneimine and is in the range of from about 500 to about 1000 Daltons, while y is
  • a coating layer over the core contains from about 1%to about 10%, by total weight of the detergent granule, of silica.
  • the present invention relates to a granular detergent composition containing from about 1%to about 99%of the above-described detergent granule.
  • the present invention relates to a method of making the above-described detergent granule, by: (a) forming aqueous paste comprising the one or more anionic surfactants, the non-quaternized alkoxylated polyethyleneimine, and water; (b) mixing the aqueous paste from step (a) with a solid carrier to form a core particle; and (c) coating silica over the core particle.
  • the term “granule” or “particle” refers to a solid matter of minute quantity, such as a powder, granule, encapsulate, microcapsule, and/or prill.
  • the granules or particles of the present invention can be spheres, rods, plates, tubes, squares, rectangles, discs, stars or flakes of regular or irregular shapes, but they are non-fibrous.
  • the granules or particles of the present invention may have a median particle size of about 2000 ⁇ m or less, as measured according to the Median Particle Size Test described herein.
  • the particles of the present invention have a median particle size ranging from about 1 ⁇ m to about 2000 ⁇ m, more preferably from about 10 ⁇ m to about 1800 ⁇ m, still more preferably from about 50 ⁇ m to about 1700 ⁇ m, still more preferably from about 100 ⁇ m to about 1500 ⁇ m, still more preferably from about 250 ⁇ m to about 1000 ⁇ m, most preferably from about 300 ⁇ m to about 800 ⁇ m, as measured according to the Median Particle Size Test described herein.
  • detergent granule or “detergent particle” refers to granules or particles containing at least one surfactant, preferably at least one anionic surfactant.
  • composite detergent granule As used herein, the term “composite detergent granule, ” “composite detergent particle, ” “hybrid detergent granule, ” or “hybrid detergent particle” refer to granules or particles containing two or more surfactants, preferably at least two anionic surfactants.
  • main surfactant refers to a surfactant which is present in an article at an amount of about 50%or more, by total weight of all surfactants in such article.
  • coating layer means a partial or complete coating of a layering material over the outer surfaces of a particulate or granular material, or at least a portion of such outer surfaces.
  • a granular detergent composition refers to a solid composition, such as granular or powder-form all-purpose or heavy-duty washing agents, e.g., for cleaning fabrics, dishes, and/or hard surface, as well as cleaning auxiliaries such as bleach, rinse aids, additives, or pre-treat types.
  • water-soluble refers to the ability of a sample material to completely dissolve in or disperse into water leaving no visible solids or forming no visibly separate phase, when at least about 25 grams, preferably at least about 50 grams, more preferably at least about 100 grams, most preferably at least about 150 grams, of such material is placed in one liter (1L) of deionized water at 20°C and under the atmospheric pressure with sufficient stirring.
  • the term "substantially free of” means that that the component of interest is present in an amount less than about 0.1%by weight.
  • the terms “consisting essentially of” means that the composition contains no ingredient that will interfere with benefits or functions of those ingredients that are explicitly disclosed. Further, the term “substantially free of” or “substantially free from” means that the indicated material is present in the amount of from 0 wt%to about 5 wt%, preferably from 0 wt%to 3 wt%. The term “essentially free of” means that the indicated material is present in the amount of from 0 wt%to about 1 wt%, preferably from 0 wt%to about 0.5 wt%, more preferably from 0 wt%to about 0.1 wt%, most preferably it is not present at analytically detectable levels.
  • flowability of highly concentrated anionic detergent granules i.e., those with anionic surfactant concentrations as high as from about 40%to about 90%, preferably from about 50%to about 80%, by total weight of the detergent granules
  • anionic surfactant concentrations as high as from about 40%to about 90%, preferably from about 50%to about 80%, by total weight of the detergent granules
  • the poor flowability in turn leads to challenges in bulk-handling of such highly concentrated anionic detergent granules during the manufacturing process.
  • the present invention has discovered that by adding a non-quaternized alkoxylated polyethyleneimine (PEI) into such highly concentrated anionic detergent granules and then forming a silica coating layer thereover can significantly improve the flowability of such detergent granules, especially when such detergent granules contain high concentrations of alkylalkoxylated sulfate (AAS) surfactant (s) .
  • PEI polyethyleneimine
  • the alkoxylated PEI functions as a surfactant structurant to increase the particle strength of the detergent granules, while the silica coating layer functions to reduce the surface stickiness of the detergent granules.
  • the alkoxylated PEI and the silica coating layer can significantly improve the flowability of the detergent granule, while flowability improvement achieved by either adding the alkoxylated PEI alone or forming the silica coating layer alone is much less significant.
  • the core of the detergent granule of the present invention may be characterized by a median particle size ranging from about 100 microns to about 900 microns, preferably from about 300 microns to about 800 microns, and more preferably from about400 microns to about 700 microns.
  • anionic Surfactant (s) First, the core of the highly concentrated anionic detergent granule of the present invention contains one or more anionic surfactants, which are present in the amount ranging from about 40%to about 90%, preferably from about 50%to about 80%, by weight of such detergent granule.
  • the one or more anionic surfactants are selected from the group consisting of: (1) a C 10 -C 20 linear or branched alkylalkoxylated sulfate (AAS) surfactant; (2) a C 6 -C 20 linear or branched unalkoxylated alkyl sulfate (AS) surfactant; (3) a C 10 -C 20 linear alkyl benzene sulphonate (LAS) surfactant; and (4) combinations thereof.
  • AAS alkylalkoxylated sulfate
  • AS unalkoxylated alkyl sulfate
  • LAS alkyl benzene sulphonate
  • the core of the highly concentrated anionic detergent granule of the present invention contains a C 10 -C 20 linear or branched alkylalkoxylated sulfate (AAS) surfactant having a weight average degree of alkoxylation ranging from about 0.1 to about 10, preferably from about 0.1 to about 5.
  • a particularly preferred AAS surfactant for the practice of the present invention is a C 12 -C 18 linear alkylethoxylated sulfate (AES) having a weight average degree of ethoxylation of from about 0.5 to about 3.0, preferably from about 0.5 to about 2, more preferably from about 0.5 to about 1. More preferably, the AAS surfactant is a C 12 -C 14 linear alkylethoxylated sulfate (AES) surfactant having a weight average degree of ethoxylation of from about 0.5 to about 1.
  • Such AAS surfactant may be present in the core in an amount ranging from about 20%to about 90%, preferably from about 30%to about 90%, more preferably from about 40%to about 80%, most preferably from about 50%to about 70%, by total weight of said core.
  • the core comprises only one surfactant, which is the AAS surfactant.
  • the core comprises two or more surfactants, but the AAS surfactant is present as the main surfactant in such core, while one or more other surfactants (anionic, nonionic, amphoteric, and/or cationic) are present as co-surfactants.
  • the core of the highly concentrated anionic detergent granule of the present invention may contain a C 10 -C 20 linear alkyl benzene sulphonate (LAS) surfactant as the anionic surfactant, either alone or in combination with the above-mentioned AAS.
  • LAS linear alkyl benzene sulphonate
  • LAS surfactants are well known in the art and can be readily obtained by sulfonating commercially available linear alkylbenzenes.
  • Exemplary C 10 -C 20 linear alkylbenzene sulfonates that can be used in the present invention include alkali metal, alkaline earth metal or ammonium salts of C 10 -C 20 linear alkylbenzene sulfonic acids, and preferably the sodium, potassium, magnesium and/or ammonium salts of C 11 -C 18 or C 11 -C 14 linear alkylbenzene sulfonic acids.
  • the sodium or potassium salts of C 12 linear alkylbenzene sulfonic acids More preferred are the sodium or potassium salts of C 12 linear alkylbenzene sulfonic acids, and most preferred is the sodium salt of C 12 linear alkylbenzene sulfonic acid, i.e., sodium dodecylbenzene sulfonate.
  • the amount of LAS in the core may range from about 5%to about 90%, preferably from about 10%to about 70%, and more preferably from about 15%to about 45%, by total weight of the core.
  • the core of the highly concentrated anionic detergent granule of the present invention contains both the AAS surfactant and the LAS surfactant, while the weight ratio of AAS to LAS ranges from about 1:3 to about 10: 1, preferably from about 1: 2 to about 8: 1, more preferably about 1: 1 to about 5: 1, most preferably from about 2: 1 to about 4: 1.
  • the core of the highly concentrated anionic detergent granule of the present invention may contain a C 10 -C 20 linear or branched unalkoxylated alkyl sulfate (AS) surfactant as the anionic surfactant, either alone or in combination with the above-mentioned AAS and/or LAS.
  • AS unalkoxylated alkyl sulfate
  • the amount of AS in the core may range from about 50%to about 90%, preferable from about 60 to about 90%, and more preferably from about 65%to about 85%by total weight of the core.
  • the core may contain additional anionic surfactants (in addition to AAS, LAS and/or AS) , such as C 10 -C 20 linear or branched alkyl sulphonates, C 10 -C 20 linear or branched alkyl phosphates, C 10 -C 20 linear or branched alkyl phosphonates, C 10 -C 20 linear or branched alkyl carboxylates, and salts and mixtures thereof.
  • additional anionic surfactants in addition to AAS, LAS and/or AS
  • anionic surfactants such as C 10 -C 20 linear or branched alkyl sulphonates, C 10 -C 20 linear or branched alkyl phosphates, C 10 -C 20 linear or branched alkyl phosphonates, C 10 -C 20 linear or branched alkyl carboxylates, and salts and mixtures thereof.
  • the core of the highly concentrated anionic detergent granule of the present invention may further contain, in addition to the above-mentioned anionic surfactants, one or more surfactants selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactant, and combinations thereof.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols.
  • the nonionic surfactant may be selected from ethoxylated alcohols and ethoxylated alkyl phenols of the formula R (OC 2 H 4 ) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • Non-limiting examples of nonionic surfactants useful herein include: C 8 -C 18 alkyl ethoxylates, such as, nonionic surfactants from Shell; C 6 -C 12 alkyl phenol alkoxylates where the alkoxylate units may be 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 from BASF; C 14 -C 22 mid-chain branched alcohols, BA; C 14 -C 22 mid-chain branched alkyl alkoxylates, BAE x , wherein x is from 1 to 30; alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxy fatty acid amides; and ether capped poly (oxyalkylated) alcohol surfactants.
  • Suitable nonionic detersive surfactants also include alkyl polyglucoside and al
  • Non-limiting examples of cationic surfactants include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; cationic ester surfactants; and amino surfactants, e.g., amido propyldimethyl amine (APA) .
  • AQA alkoxylate quaternary ammonium
  • APA amido propyldimethyl amine
  • Suitable cationic detersive surfactants also include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
  • Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula:
  • 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
  • suitable anions include: halides, for example chloride; sulphate; and sulphonate.
  • Suitable cationic detersive surfactants are mono-C 6-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides.
  • Highly suitable 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.
  • Suitable examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, including derivatives of heterocyclic secondary and tertiary amines; derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds; betaines, including alkyl dimethyl betaine, cocodimethyl amidopropyl betaine, and sulfo and hydroxy betaines; C 8 to C 18 (preferably from C 12 to C 18 ) amine oxides; N-alkyl-N, N-dimethylammino-1-propane sulfonate, where the alkyl group can be C 8 to C 18 .
  • Suitable amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight or branched-chain and where one of the aliphatic substituents contains at least about 8 carbon atoms, or from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.
  • Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof.
  • Non-quaternized Alkoxylated Polyethyleneimine contains, in addition to the anionic surfactants as described hereinabove, a non-quaternized alkoxylated polyethyleneimine having a polyalkyleneimine core with one or more alkoxy side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, which may be present in the amount ranging from about 0.5%to about 10%, preferably from about 1%to about 5%, by total weight of the detergent granule.
  • the non-quaternized alkoxylated polyalkyleneimine is uncharged.
  • the alkoxylated polyethyleneimine is typically non-quaternized at the pH of the concentrated surfactant composition.
  • the non-quaternized alkoxylated polyethyleneimine may be linear, branched, or combinations thereof, preferably branched.
  • the non-quaternized alkoxylated polyalkyleneimine has a polyalkyleneimine (PEI) core with one or more alkoxy side chains bonded to at least one nitrogen atom in the polyalkyleneimine core.
  • PEI polyalkyleneimine
  • the non-quaternized alkoxylated polyethyleneimine comprises a polyalkyleneimine backbone.
  • the polyalkyleneimine may comprise C 2 alkyl groups, C 3 alkyl groups, or mixtures thereof, preferably C 2 alkyl groups.
  • the non-quaternized alkoxylated polyethyleneimine polymer may have a polyethyleneimine ( “PEI” ) backbone.
  • the PEI backbone may have an average number-average molecular weight of from about 400 to about 1000, or from about 500 to about 750, or from about 550 to about 650, or about 600 Daltons, as determined prior to ethoxylation.
  • the PEI backbone of the polymers described herein, prior to alkoxylation, may have the general empirical formula:
  • n+m is equal to or greater than 8, or 10, or 12, or 14, or 18, or 22.
  • the non-quaternized alkoxylated polyethyleneimine typically comprises alkoxylated nitrogen groups.
  • the non-quaternized alkoxylated polyethyleneimine may independently comprise, on average per alkoxylated nitrogen, up to about 50, or up to about 40, or up to about 35, or up to about 30, or up to about 25, or up to about 20, alkoxylate groups.
  • the non-quaternized alkoxylated polyethyleneimine may independently comprise, on average per alkoxylated nitrogen, at least about 5, or at least about 10, or at least about 15, or at least about 20, alkoxylate groups.
  • the alkoxylate groups may be ethoxylate (EO) groups, propoxylate (PO) groups, or combinations thereof, but are preferably ethoxylate (EO) groups.
  • the non-quaternized alkoxylated polyethyleneimine may comprise on average per alkoxylated nitrogen, about 1-50 ethoxylate (EO) groups and about 0-50 propoxylate (PO) groups.
  • the non-quaternized alkoxylated polyethyleneimine may comprise on average per alkoxylated nitrogen, about 1-50 ethoxylate (EO) groups and is free of propoxylate (PO) groups.
  • the non-quaternized alkoxylated polyethyleneimine may comprise on average per alkoxylated nitrogen, about 10-30 ethoxylate (EO) groups, preferably about 15-25 ethoxylate (EO) groups.
  • Suitable non-quaternized alkoxylated polyethyleneimine may include propoxylated polyalkylenimine (e.g., PEI) polymers.
  • the propoxylated polyalkylenimine (e.g., PEI) polymers may also be ethoxylated.
  • the propoxylated polyalkylenimine (e.g., PEI) polymers may have inner polyethylene oxide blocks and outer polypropylene oxide blocks, the degree of ethoxylation and the degree of propoxylation not going above or below specific limiting values.
  • the ratio of polyethylene blocks to polypropylene blocks (n/p) may be from about 0.6, or from about 0.8, or from about 1, to a maximum of about 10, or a maximum of about 5, or a maximum of about 3.
  • the n/p ratio may be about 2.
  • the propoxylated polyalkylenimines may have PEI backbones having weight average molecular weights (as determined prior to alkoxylation) of from about 200 g/mol to about 1200 g/mol, or from about 400 g/mol to about 800 g/mol, or about 600 g/mol.
  • the molecular weight of the propoxylated polyalkylenimines may be from about 8,000 to about 20,000 g/mol, or from about 10,000 to about 15,000 g/mol, or about 12,000 g/mol.
  • Suitable propoxylated polyalkylenimine polymers may include compounds of the following structure:
  • EOs are ethoxylate groups and POs are propoxylate groups.
  • the compound shown above is a PEI where the molar ratio of EO: PO is about 10: 5 (e.g., 2: 1) .
  • Other similar, suitable compounds may include EO and PO groups present in a molar ratio of about 10: 5 or about 24: 16.
  • Suitable polyamines include low molecular weight, water soluble, and lightly alkoxylated ethoxylated/propoxylated polyalkyleneamine polymers.
  • lightly alkoxylated it is meant the polymers of this invention average from about 0.5 to about 20, or from 0.5 to about 10, alkoxylations per nitrogen.
  • the polyamines may be “substantially noncharged, ” meaning that there are no more than about 2 positive charges for every about 40 nitrogens present in the backbone of the polyalkyleneamine polymer at pH 10, or at pH 7; it is recognized, however, that the charge density of the polymers may vary with pH.
  • Suitable alkoxylated polyalkyleneimines such as PEI 600 EO 20 , are available from BASF (Ludwigshafen, Germany) .
  • Ethylene oxide-propylene oxide-ethylene oxide (EO/PO/EO) triblock copolymer The core of the highly concentrated anionic detergent granule of the present invention may further contain, in addition to the anionic surfactants and the PEI polymers mentioned hereinabove, an ethylene oxide-propylene oxide-ethylene oxide (EO/PO/EO) triblock copolymer, which preferably has an average propylene oxide chain length of between about 20 and about 70, preferably between about 30 and about 60, more preferably between about 45 and about 55 propylene oxide units.
  • the ethylene oxide-propylene oxide-ethylene oxide (EO/PO/EO) triblock copolymer has a weight average molecular weight of between about 1000 and about 10,000, preferably between about 1500 and about 5000 more preferably between about 2000 and about 4500, even more preferably between about 2500 and about 4000, most preferably between about 3500 and about 3800 Daltons.
  • each ethylene oxide block or chain independently has an average chain length of between about 2 and about 90, preferably about 3 and about 50, more preferably between about 4 and about 20 ethylene oxide units.
  • the copolymer comprises between about 10%and about 90%, preferably between about 15%and about 50%, most preferably between about 15%and about 25%by weight of the copolymer of the combined ethylene-oxide blocks.
  • the total ethylene oxide content is equally split over the two ethylene oxide blocks. Equally split herein means each ethylene oxide block comprising on average between about 40%and about 60%preferably between about 45%and about 55%, even more preferably between about 48%and about 52%, most preferably about 50%of the total number of ethylene oxide units, the %of both ethylene oxide blocks adding up to 100%.
  • the copolymer has a weight average molecular weight between about 3500 and about 3800 Daltons, a propylene oxide content between about 45 and about 55 propylene oxide units, and an ethylene oxide content of between about 4 and about 20 ethylene oxide units per ethylene oxide block.
  • Suitable ethylene oxide –propylene oxide –ethylene oxide triblock copolymers are commercially available under the Pluronic PE series from the BASF company, or under the Tergitol L series from the Dow Chemical Company.
  • a particularly suitable material is Pluronic PE 9200.
  • the core of the highly concentrated anionic detergent granule of the present invention may contain a solid carrier selected from the group consisting of: zeolite, silica, carboxymethyl cellulose, modified starch, and combinations thereof.
  • a solid carrier selected from the group consisting of: zeolite, silica, carboxymethyl cellulose, modified starch, and combinations thereof.
  • such solid carrier is present in an amount ranging from about 5%to about 50%, preferably from about 15%to about 45%, more preferably from about 20%to about 30%, by total weight of the detergent granule.
  • the solid carrier is silica, and more preferably hydrophilic silica.
  • Silica has both internal and external surface area, which allows for easy absorption of liquids and has a large liquid loading capacity.
  • Hydrophilic silica is especially effective at adsorbing water.
  • Any silica particles with suitable particle sizes can be employed for practice of the present invention.
  • the silica particles have a dry particle size distribution Dw50 ranging from about 0.1 ⁇ m to about 100 ⁇ m, preferably from about 1 ⁇ m to about 50 ⁇ m, more preferably from about 2 ⁇ m to about 40 ⁇ m, and most preferably from 4 ⁇ m to about 20 ⁇ m.
  • the silica particles are composed of hydrophilic silica that can be hydrated upon contact with the washing liquor to expand volumetrically.
  • hydrophilic silica and preferably precipitated hydrophilic silica, is incorporated into the core of the detergent granule of the present invention together with anionic surfactants therein to provide higher surfactant activity and faster dispersion or dissolution benefits.
  • a particularly preferred hydrophilic precipitated silica material for practice of the present invention is commercially available from Evonik Corporation under the tradename
  • the silica is preferably present in the core of the detergent granules in an amount ranging from about 10 wt%to about 50 wt%, more preferably from about 15 wt%to about 45 wt%, and most preferably from about 20 wt%to about 30 wt%, by total weight of the detergent granules.
  • the core of the highly concentrated anionic detergent granule of the present invention may contain a water-soluble inorganic salt selected from the group consisting of sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and combinations thereof.
  • a water-soluble inorganic salt selected from the group consisting of sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and combinations thereof.
  • Particularly preferred examples of water-soluble inorganic salts for the practice of the present invention include sodium sulfate and sodium carbonate, while sodium sulfate is most preferred.
  • Such water-soluble inorganic salt may be present in an amount ranging from about 1%to about 20%, preferably from about 2%to about 15%, more preferably from about 3%to about 10%, by total weight of the detergent granule.
  • particle size of the salt (s) may be reduced by a milling, grinding or a comminuting step with any apparatus known in the art for milling, grinding or comminuting of granular or particulate compositions.
  • the core may, but do not need to, further comprise one or more other cleaning actives, such as chelants, polymers, enzymes, bleaching agents, and the like.
  • the core of the highly concentrated anionic detergent granule of the present invention is substantially free of such other cleaning actives.
  • a coating layer containing silica is formed over the core of the detergent granule of the present invention.
  • Such coating layer may cover only a portion of the core, or the entire outer surface of the core.
  • the coating layer is preferably a continuous layer, but it can also be discontinuous and covering discrete regions of the outer surface of the core.
  • Such a coating layer of silica may be present in an amount ranging from about 1%to about 10%, preferably from about 2%to about 5%, by total weight of the detergent granule.
  • the silica used for forming the coating layer may be the same or different from the silica used as the solid carrier in the core.
  • the silica in the coating layer is the same as that used in the core.
  • the silica in the coating layer is hydrophilic silica, especially precipitated hydrophilic silica.
  • a particularly preferred hydrophilic precipitated silica material for practice of the present invention is commercially available from Evonik Corporation under the tradename
  • the detergent granule of the present invention may have a particle size distribution such that the D50 is from greater than about 150 micrometers to less than about 1700 micrometers.
  • the detergent granule may have a particle size distribution such that the D50 is from greater than about 212 micrometers to less than about 1180 micrometers.
  • the detergent granule may have a particle size distribution such that the D50 is from greater than about 300 micrometers to less than about 850 micrometers.
  • the detergent granule may have a particle size distribution such that the D50 is from greater than about 350 micrometers to less than about 700 micrometers.
  • the detergent granule may have a particle size distribution such that the D20 is greater than about 150 micrometers and the D80 is less than about 1400 micrometers.
  • the detergent granule may have a particle size distribution such that the D20 is greater than about 200 micrometers and the D80 is less than about 1180 micrometers.
  • the detergent granule may have a particle size distribution such that the D20 is greater than about 250 micrometers and the D80 is less than about 1000 micrometers.
  • the detergent granule may have a particle size distribution such that the D10 is greater than about 150 micrometers and the D90 is less than about 1400 micrometers.
  • the detergent granule may have a particle size distribution such that the D10 is greater than about 200 micrometers and the D90 is less than about 1180 micrometers.
  • the detergent granule may have a particle size distribution such that the D10 is greater than about 250 micrometers and the D90 is less than about 1000 micrometers.
  • the detergent granule may be used in a bead-like detergent or derivative thereof.
  • the detergent granule may have a particle size distribution such that the D50 is from greater than about 1mm to less than about 4.75mm.
  • the detergent granule may have a particle size distribution such that the D50 is from greater than about 1.7mm to less than about 3.5mm.
  • the detergent granule may have a particle size distribution such that the D20 is greater than about 1mm and the D80 is less than about 4.75mm.
  • the detergent granule may have a particle size distribution such that the D20 is greater than about 1.7mm and the D80 is less than about 3.5mm.
  • the detergent granule may have a particle size distribution such that the D10 is greater than about 1mm and the D90 is less than about 4.75mm.
  • the detergent granule may have a particle size distribution such that the D10 is greater than about 1.7mm and the D90 is less than about 3.5mm.
  • the bulk density of such detergent granule may range from about 300g/L to about 900 g/L, preferably from about 400g/L to about 800g/L, more preferably from about 450g/L to about 550g/L.
  • the detergent granule of the present invention preferably has a total moisture content of no more than about 5%, preferably no more than about 3%, more preferably no more than about 2.5%, by total weight of such detergent granule.
  • detergent granules are particularly useful for forming high active granular detergent compositions of improved water hardness resistance, fast surfactant release and better dissolution or dispersion.
  • Such detergent granules may be provided in a granular detergent composition in an amount ranging from about 1%to about 99%, preferably from about 2%to about 80%, and more preferably from about 5%to about 50%by total weight of the granular detergent composition.
  • the granular detergent composition may comprise one or more additional surfactants that are added directly therein, i.e., independent of the detergent granules as described hereinabove.
  • the additional surfactants can be same as those already included in the detergent granules, or they can be different.
  • the same types of anionic surfactants and other surfactants as described hereinabove are also suitable for directly addition into the granular detergent composition.
  • the granular detergent compositions of the present invention may further comprise a water-swellable cellulose derivative.
  • Suitable examples of water-swellable cellulose derivatives are selected from the group consisting of substituted or unsubstituted alkyl celluloses and salts thereof, such as ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, carboxyl methyl cellulose (CMC) , cross-linked CMC, modified CMC, and mixtures thereof.
  • such cellulose derivative materials can rapidly swells up within about 10 minutes, preferably within about 5 minutes, more preferably within about 2 minutes, even more preferably within about 1 minute, and most preferably within about 10 seconds, after contact with water.
  • the water-swellable cellulose derivatives can be incorporated into the structured particles of the present invention together with the hydrophilic silica, or they can be incorporated into the granular detergent compositions independent of the structured particles, in an amount ranging from about 0.1%to about 5%and preferably from about 0.5%to about 3%. Such cellulose derivatives may further enhance the mechanical cleaning benefit of the granular detergent compositions of the present invention.
  • the granular detergent compositions may optionally include one or more other detergent adjunct materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.
  • detergent adjunct materials include: (1) inorganic and/or organic builders, such as carbonates (including bicarbonates and sesquicarbonates) , sulphates, phosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates) , phosphonates, phytic acid, silicates, zeolite, citrates, polycarboxylates and salts thereof (such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1, 3, 5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof) , ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,
  • N-alkylated amino triazines propylene oxide, monostearyl phosphates, silicones or derivatives thereof, secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils;
  • suds boosters such as C 10 -C 16 alkanolamides, C 10 -C 14 monoethanol and diethanol amides, high sudsing surfactants (e.g., amine oxides, betaines and sultaines) , and soluble magnesium salts (e.g., MgCl 2 , MgSO 4 , and the like)
  • fabric softeners such as smectite clays, amine softeners and cationic softeners
  • dye transfer inhibiting agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
  • the detergent granules of the present invention can be formed by well-known processes, preferably by agglomeration processes using suitable mixing devices known in the art. Any suitable mixing apparatus capable of handling viscous paste can be used as the mixer described hereinabove for practice of the present invention. Suitable apparatus includes, for example, high-speed pin mixers, ploughshare mixers, paddle mixers, twin-screw extruders, Teledyne compounders, etc. The mixing process can either be carried out intermittently in batches or continuously.
  • the detergent granule is formed in at least two steps, including a first step of forming the core and then a second step of forming the silica coating layer over the core.
  • the detergent granule is formed in at least three steps, including a first step of forming an aqueous paste comprising the one or more anionic surfactants, the non-quaternized alkoxylated polyethyleneimine, and water; a second step of mixing the aqueous paste from the first step with a solid carrier to form a core particle; and a third step of coating silica over said core particle to form the coating layer.
  • the detergent granule of the present invention is formed according to a paste-agglomeration process, which comprises the steps of: (a) adding powder raw ingredients into a mixer-granulator, wherein the powder raw ingredients may comprise one or more solid carriers, water-soluble inorganic salts, buffers, dispersant polymers or chelants, necessary powder process aides, and fines recycled from the agglomeration process; (b) adding a paste comprising a premix of concentrated anionic surfactants (i.e., AAS and/or LAS, optionally with other surfactants) and the non-quaternized alkoxylated polyethyleneimine (optionally with the ethylene oxide-propylene oxide-ethylene oxide (EO/PO/EO) triblock copolymer) ; (c) running the mixer-granulator to provide a suitable mixing flow field to disperse the paste with the powder and form agglomerates; and (d) adding additional powder ingredients (i.e., silica and optionally other dry powders
  • LAS surfactant When LAS surfactant is included in the detergent granule, it is preferably added in a stream that is separate from the pre-mixed surfactant paste containing AAS.
  • Process options include adding pre-neutralized LAS as a solid powder in step (a) , adding a neutralized or partially-neutralized LAS paste as a supplement in step (b) , or adding a liquid acid precursor (HLAS) as a supplement in step (b) . In the latter cases, sufficient free alkalinity must be present in the powders added in step (a) to effectively neutralize the HLAS during the agglomeration process.
  • HLAS neutralization may be done in a separate pre-processing step, first premixing HLAS with alkaline buffer powder ingredients and other optional solid carriers to form a neutralized pre-mix of LAS and alkaline buffer powder in a powder form, and then adding said premix in step (a) above.
  • a concentrated aqueous paste comprising a mixture of AAS surfactant and the non-quaternized alkoxylated polyethyleneimine, an extrusion process may be used.
  • the extrusion process comprises the steps of (a) optionally adding fine powder to said paste, dispersing the powder into the paste to form a stiffer paste; (b) extruding the paste mixture through die plate openings of suitable size for the desired particle size, forming extrudates; (c) dividing said extrudates into particles by direct cutting of extrudates upon their exit from the die opening or by breakage in an agitated mixer following the extrusion process; (d) optionally rounding the particles in a spheronization process to form sphere-like particles; (e) optionally drying the resultant particles in a fluidized-bed dryer to remove excess moisture; (f) optionally cooling particles in a fluidized bed cooler; (g) removing any excess fine particles from the particle size distribution, preferably by elutriation from the fluidized beds of steps (e) and/or (f) , and recycling fines back to step (a) ; (h) removing excess oversize particles from the particle size distribution, preferably by screen classification; (i
  • the non-quaternized alkoxylated polyethyleneimine detergent granule comprises the steps of: (a) adding powder raw materials into a mixer-granulator wherein the powder comprises AAS surfactant in a fine powder form, optionally with additional solid carriers, water-soluble inorganic salts, buffers, dispersant polymers or chelants, necessary powder process aides, and fines recycled from the granulation process; (b) adding a binder comprising the non-quaternized alkoxylated polyethyleneimine; (c) running the mixer-granulator to provide a suitable mixing flow field to disperse the binder with the powder, forming agglomerates; optionally, (d) adding additional powder ingredients (i.e., silica and other dry powder ingredients) to at least partially coat the agglomerates, forming the coating layer; (e) optionally drying the resultant agglomerates in a fluidized-bed dryer to remove excess moisture; (f)
  • additional powder ingredients i.e., silica
  • the initial particle size of the powder material comprising surfactant has a D50 particle size less than about 100 micrometers and a D90 particle size less than about 200 micrometers, more preferably a D50 particle size less than about 50 micrometers and a D90 particle size less than about 100 micrometers.
  • a pre-grinding step may be added to achieve a finer surfactant-containing powder material.
  • surfactant-containing materials may be combined with other dry materials such as builders and buffers. Alternatively, cryogenic grinding of surfactant-containing materials may be used. Examples of particles made using this process are given in the Example section.
  • Concentrated surfactant pastes are intermediate compositions that may be combined with other ingredients to form the detergent granule of the current invention.
  • Concentrated surfactant compositions may comprise, may consist essentially of, or may consist of the following components: a surfactant system that may include an AAS surfactant and/or a LAS surfactant; an alkoxylated amine, preferably an alkoxylated polyamine; an organic solvent system; and water.
  • the concentrated surfactant composition may comprise: from about 70%to about 90%, by weight of the composition, of a surfactant system, where the surfactant system comprises from about 50%, or from about 60%, or from about 70%, or from about 80%, to about 100%, of AAS surfactant; from about 0.1%to about 25%, by weight of the composition, of an alkoxylated polyethyleneimine (PEI) ; less than about 5%, by weight of the composition, of an organic solvent system; and water.
  • PEI alkoxylated polyethyleneimine
  • the granular detergent composition which is provided in a finished product form, can be made by mixing the detergent granules of the present invention with a plurality of other particles containing the above-described additional surfactants, cellulose derivatives, and detergent adjunct materials.
  • Such other particles can be provided as spray-dried particles, agglomerated particles, and extruded particles.
  • the additional surfactants, cellulose derivatives, and detergent adjunct materials can also be incorporated into the granular detergent composition in liquid form through a spray-on process.
  • the granular detergent compositions of the present invention can be used for either machine washing or hand washing of fabrics. It is particularly suitable for use in a hand-washing context.
  • the laundry detergent is typically diluted by a factor of from about 1: 100 to about 1: 1000, or about 1: 200 to about 1: 500 by weight, by placing the laundry detergent in a container along with wash water to form a laundry liquor.
  • the wash water used to form the laundry liquor is typically whatever water is easily available, such as tap water, river water, well water, etc.
  • the temperature of the wash water may range from about 0°C to about 40°C, preferably from about 5°C to about 30°C, more preferably from about 5°C to about 25°C, and most preferably from about 10°C to about 20°C, although higher temperatures may be used for soaking and/or pretreating.
  • the laundry detergent and wash water is usually agitated to evenly disperse and/or either partially or completely dissolve the detergent and thereby form a laundry liquor. Such agitation forms suds, typically voluminous and creamy suds.
  • the dirty laundry is added to the laundry liquor and optionally soaked for a period of time. Such soaking in the laundry liquor may be overnight, or for from about 1 minute to about 12 hours, or from about 5 minutes to about 6 hours, or from about 10 minutes to about 2 hours.
  • the laundry is added to the container either before or after the wash water, and then the laundry detergent is added to the container, either before or after the wash water.
  • the method herein optionally includes a pre-treating step where the user pre-treats the laundry with the laundry detergent to form pre-treated laundry.
  • the laundry detergent may be added directly to the laundry to form the pre-treated laundry, which may then be optionally scrubbed, for example, with a brush, rubbed against a surface, or against itself before being added to the wash water and/or the laundry liquor.
  • the diluting step may occur as the laundry detergent from the pre-treated laundry mixes with the wash water to form the laundry liquor.
  • the laundry is then hand-washed by the user who may or may not use one or more hand-held washing devices, such as washboards, brushes, or rods.
  • the actual hand-washing duration may range from about 10 seconds to about 30 minutes, preferably from about 30 seconds to about 20 minutes, more preferably from about 1 minute to about 15 minutes, and most preferably from about 2 minutes to about 10 minutes.
  • the laundry may be wrung out and put aside while the laundry liquor is either used for additional laundry, poured out, etc.
  • the rinse water is then added to form a rinse bath, and then it is common practice to agitate the laundry to remove the surfactant residue.
  • the laundry may be soaked in the rinse water and then wrung out and put aside.
  • the number of rinses when using the liquid laundry detergent herein is typically from about 1 to about 3, or from about 1 to about 2. In a particularly preferred embodiment of the present invention, the rinse is carried out in a single rinse step or cycle.
  • the particle size distribution of the detergent granule is determined by using ASTM D 502 –89, “Standard Test Method for Particle Size of Soaps and Other Detergents” , approved May 26, 1989, with a further specification for sieve sizes and sieve time used in the analysis.
  • ASTM D 502 –89 Standard Test Method for Particle Size of Soaps and Other Detergents
  • a nest of clean dry sieves 1400 micrometer, 1180 micrometer, 850 micrometer, 600 micrometer, 425 micrometer, 250 micrometer, 150 micrometer, is required to cover the range of particle sizes referenced herein.
  • the prescribed machine-sieving method is used with the above sieve nest.
  • a suitable sieve-shaking machine can be obtained from W. S. Tyler Company, Ohio, U.S.A.
  • the sieve-shaking test sample is approximately 100 grams and is shaken for 5 minutes.
  • a characteristic particle size (Dx) for the purpose of this invention, is defined as the abscissa value at the point where the cumulative mass percent is equal to x percent, and is calculated by a straight-line interpolation between the data points directly above (a) and below (b) the x%value using the following equation:
  • Example 1 Exemplary Detergent Granule Formulations:
  • sample detergent granules including: (1) a control sample ( “Control” ) that contains neither the alkoxylated PEI polymer nor the silica coating layer; (2) a first comparative sample ( “C1” ) that contains only the alkoxylated PEI polymer in the core, but without the silica coating layer; (3) a second comparative sample ( “C2” ) that contains only the silica coating layer, but no alkoxylated PEI polymer in the core; and (4) an inventive samples ( “S1” ) that contain both the alkoxylated PEI polymer in the core and the silica coating layer.
  • the formulations of such sample detergent granules are listed as follows:
  • the sample detergent granules as listed hereinabove can be made by a suitable binder-agglomeration process.
  • the process can be batch or continuous.
  • the particle size distribution is one of the key factors influencing particle flowability. Therefore, it is important to ensure that all sample detergent granules have the same or substantially similar particle size distributions, in order to minimize any potential impact of the particle size distribution variations on the flowability test results.
  • the same or substantially similar particle size distribution for all sample detergent granules can be obtained by sieving the sample detergent granules with a nest of clean dry sieves using a sieve-shaking machine. The sieved samples from each sieve can then be combined to form a sample detergent granule characterized by a desired particle size distribution. For example, all sample detergent granules tested herein are all characterized by a D50 of approximately 614 micrometers, measured by Test 2 described hereainabove.
  • each of the sample detergent granules is left in an open petri dish as a thin layer under the ambient condition (20-22°C and 35-40%RH) to allow them to absorb moisture from the ambience for about 1 day.
  • the samples need to reach an eRH of 30-35%before running the flowability test.
  • the flowability (ff c ) of each sample detergent granule is the ratio of ⁇ 1 (consolidation stress) to ⁇ c (unconfined yield strength) , which is used to characterize flowability numerically: the larger ffc means the better a bulk solid flows.
  • the flowability (ff c ) data is generated from a Schulze Ring Shear Tester RST-XS (as shown in FIG. 1) , while the detailed test procedure of the ring shear tester is described in detail in ASTM standard D-6773.
  • the consolidation stress at pre-shear is set as 16000Pa, and five different other consolidation stresses (3200Pa, 4800Pa, 6400Pa, 8000Pa and 9600Pa) are also applied during the same test.
  • the minimum shear stress required to shear the bulk sample (shear to failure) at each consolidation stress is then measured to generate a yield locus (see Fig 4.10 in D. Schulze, Powder and Bulk Solid: Behavior, Characterization, Storage and Flow, Springer, 2008) .
  • the yield locus is then used to calculate the consolidation stress, ⁇ 1 and the unconfined yield strength, ⁇ c; and the ratio of ⁇ 1 to ⁇ c is the flowability, ff c . Following are the flowability test results of the sample detergent granules:
  • the above flowability data shows that the combination of alkoxylated PEI polymer in the core and the silica coating thereover in the inventive sample detergent granule S1 surprisingly and unexpected improves the flowability of such detergent granule, significantly above the flowability improvement observed by either adding the alkoxylated PEI polymer alone or providing the silica coating layer alone.
  • Example 2 The four (4) sample detergent granules of Example 2 (i.e., control, C1, C2 and S1) are also subjected to the following compressive force test:
  • a suitable mechanical testing machine (INSTRON 3369 with compaction platens and a punch and die set to measure compression up to at least 10 MPa pressure) is used. Put the bottom punch into the die. Add a sufficient sample of detergent granules (250-850 ⁇ m) into the die, to form a tablet having a height to diameter ratio of from about 0.2 to about 0.5. Add the top punch gently until it rests on the powder. Put the die and punch between the platens of the mechanical testing machine. Move the top platen to less than about 1mm from the top of the punch. Execute a compressive test to a force that is equivalent to a pressure limit of at least 10 MPa. After compression, retract the platen, remove die and punch, eject the tablet, and measure the height and mass of the tablet.
  • the compaction curve recoded in the system can be used to calculate yield stress data following below procedure:
  • the compaction curve onset calculation is done by taking tangent lines from particle re-arrangement region to particle deformation region, positioned close to the transition in the curve, and solving for the intersection of the tangents.
  • the first derivative of the compaction curve is used to position the tangent points at each side end of the slope transition.
  • the apparent yield stress can be defined by this onset analysis.
  • MPa apparent yield stress

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Abstract

L'invention concerne un granulé détergent ayant une teneur totale en tensioactif anionique relativement élevée, par exemple, de 40 % à 90 % en poids total dudit granulé détergent, qui comprend un noyau et une couche de revêtement sur celui-ci. Le noyau contient un ou plusieurs tensioactifs anioniques et une polyéthylèneimine alcoxylée non quaternisée ayant un noyau de polyalkylèneimine avec une ou plusieurs chaînes latérales alcoxy liées à au moins un atome d'azote dans le noyau de polyalkylèneimine. La couche de revêtement contient de la silice. Un tel granulé détergent peut conserver une aptitude à l'écoulement satisfaisante, malgré sa teneur en tensioactif anionique élevée, ce qui facilite le traitement pour obtenir des produits détergents granulaires finis.
PCT/CN2018/074284 2018-01-26 2018-01-26 Granulés détergents ayant une teneur en tensioactif anionique élevée WO2019144372A1 (fr)

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EP18902635.4A EP3743504B1 (fr) 2018-01-26 2018-01-26 Granulés détergents ayant une teneur en tensioactif anionique élevée
PCT/CN2018/074284 WO2019144372A1 (fr) 2018-01-26 2018-01-26 Granulés détergents ayant une teneur en tensioactif anionique élevée
CN201880083216.5A CN111511890B (zh) 2018-01-26 2018-01-26 具有高阴离子表面活性剂含量的洗涤剂颗粒

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