EP1149145A1 - Granules d'enzymes basse densite et compositions en integrant - Google Patents

Granules d'enzymes basse densite et compositions en integrant

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Publication number
EP1149145A1
EP1149145A1 EP00904654A EP00904654A EP1149145A1 EP 1149145 A1 EP1149145 A1 EP 1149145A1 EP 00904654 A EP00904654 A EP 00904654A EP 00904654 A EP00904654 A EP 00904654A EP 1149145 A1 EP1149145 A1 EP 1149145A1
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EP
European Patent Office
Prior art keywords
alkyl
compositions
surfactant
surfactants
laundry detergent
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.)
Withdrawn
Application number
EP00904654A
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German (de)
English (en)
Inventor
Mark Allen Smerznak
Walter August Maria Broeckx
James Pyott Johnston
Abdennaceur Fredj
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
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
Publication of EP1149145A1 publication Critical patent/EP1149145A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • This invention relates to laundry detergent products, such as heavy duty aqueous and/or non-aqueous and/or gelled liquid laundry detergents and powder laundry detergents, which include one or more enzyme granulates comprising one or more enzyme granulate density-reducing components and one or more enzymes, and optionally one or more conventional cleaning adjunct materials.
  • laundry detergent products such as heavy duty aqueous and/or non-aqueous and/or gelled liquid laundry detergents and powder laundry detergents, which include one or more enzyme granulates comprising one or more enzyme granulate density-reducing components and one or more enzymes, and optionally one or more conventional cleaning adjunct materials.
  • Enzyme granulate as used herein is meant to encompass any solid form into which one or more enzymes are physically and/or chemically incorporated.
  • enzyme granulates are low-dusting, free-flowing granules, with a diameter between about 200 and lOOO ⁇ m.
  • Such enzyme granulates can be formed by any suitable granulation process.
  • the enzyme granulate may be a T-granulate, such as the T- granulates made by the process described in U.S. Patent Nos. 4,106,991, 4,661,452 and 4,876,198 all to Novo Nordisk A/S; a granulate made by the spray-chilling or prilling process as described by H. A. Herrmann, I. Good, A.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase variant of the protease described in WO95/10591, having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally-occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lent
  • proteases are described in PCT publications: WO 95/30010; WO 95/30011 ; and WO 95/29979.
  • Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVLNASE®, EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).
  • Other particularly useful proteases are multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 1 16, 117, 1 19, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166,
  • protease variant includes a substitution set selected from the group consisting of:
  • the protease variant includes a substitution set selected from the group consisting of:
  • the protease variant includes the substitution set 101/103/104/159/232/236/245/248/252, preferably 101 G/l 03 A 1041/159D/232V/ 236H/245R/248D/252K.
  • enzymes and their directly linked inhibitors e.g., protease and its inhibitor linked by a peptide chain as described in WO 98/13483 A
  • enzymes and their non-linked inhibitors used in selected combinations herein include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.
  • the preferred enzymes herein can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • WO94/02597 describes laundry compositions which incorporate mutant amylases. See also WO95/10603.
  • Other amylases known for use in laundry compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1,296,839 (Novo).
  • the isoelectric point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase in isoelectric point may help to improve compatibility with anionic surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e.g. additional salt bridges and enforcing calcium binding sites to increase chelant stability.
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials are also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, and in U.S. 4,507,219. Enzyme materials particularly useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868.
  • the enzyme granulates of the present invention can be made by any conventional granulation process known in the art, including but not limited to fluid-bed agglomeration/coating; mechanical agglomeration; extrusion; spray-drying; etc. Further, the enzyme granulate density-reducing components of the present invention may be incorporated into the enzyme granulates of the present invention at any step in the granulation process.
  • the T-granulation process consists of (1) an agglomerator, preferably a "ploughshare” type mixer or Schugi type mixer with horizontal or vertical shafts, equipped with blenders, wherein fibrous cellulose is agglomerated with enzymes; and optionally, (2) a top-spray fluid bed coater, wherein the enzyme granulate produced from step (1) is coated with protective coatings, such as PEG 4000, TiO 2 , and sodium thiosulfate.
  • protective coatings such as PEG 4000, TiO 2 , and sodium thiosulfate.
  • the enzyme granulate density-reducing components of the present invention may be incorporated into the enzyme granulates during the agglomeration step or the coating step of the T-granulation process, preferably the agglomeration step.
  • Another preferred granulation process is the fluidized bed top-spray coating process, an example of which is described in U.S. Patent No. 5,324,649 to Genencor International.
  • the fluidized bed top-spray coating process consists of suspending one or more sugar particles (300-500 ⁇ m) in the coater with the use of air, and then coating the sugar particles with various layers of materials, such as a sugar/starch layer, an enzyme solution layer, another sugar/starch layer and a polymeric layer.
  • the enzyme granulate density- reducing components may be incorporated into the enzyme granulates at any step and at any layer in this process.
  • cleaning adjunct materials are readily made by considering the surface, item or fabric to be cleaned, and the desired form of the composition for the laundry conditions during use (e.g., through the wash detergent use).
  • compatible means the cleaning adjunct materials do not reduce the enzymatic activity of the enzymes in the enzyme granulates to such an extent that the enzymes are not effective as desired during normal use situations.
  • suitable cleaning adjunct materials include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, dye transfer agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, perservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, processing aids, pigments and pH control agents as described in U.S. Patent Nos. 5,70
  • cleaning adjunct materials are not compatible with the enzymes in the enzyme granulates within the laundry compositions, then suitable methods of keeping the cleaning adjunct materials and the enzymes in the enzyme granulates separate (not in contact with each other) until combination of the two components is appropriate can be used. Suitable methods can be any method known in the art, such as gelcaps, encapulation, tablets, physical separation, etc.
  • an effective amount of one or more enzyme granulates described above are included in compositions useful for laundering a variety of fabrics in need of cleaning.
  • "effective amount of one or more enzyme granulates” refers to the quantity of enzyme granulates of the present invention described hereinbefore necessary to achieve the enzymatic activity necessary in the specific laundry composition.
  • Such effective amounts are readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular enzyme used, the laundry application, the specific composition of the laundry composition, and whether a liquid or dry (e.g., granular, powder) composition is required, and the like.
  • the laundry detergent compositions of the present invention comprise:
  • a laundry detergent composition of the present invention comprises one or more enzyme granulates of the present invention such that the density difference between the density of the laundry detergent composition and the density of the enzyme granulates is less than about 0.2 g/mL, more preferably less than about 0.1 g/mL, most preferably less than about 0.05 g/mL.
  • the laundry compositions comprise from about 0.0001%, preferably from about 0.001%, more preferably from about 0.01% by weight of the laundry compositions of one or more enzyme granulates of the present invention, to about 10%, preferably to about 1%, more preferably to about 0.1 %.
  • the enzyme granulates of the present invention comprise one or more enzymes of the present invention such that the enzymes are present in the laundry compositions of the present invention at a level of from about 0.0001% to about 2%, more preferably from about 0.001 % to about 2%, most preferably from about 0.01% to about 1% of pure enzyme by weight of the laundry composition.
  • laundry compositions wherein the enzyme granulates of the present invention may be employed are discussed in further detail below.
  • the laundry compositions may include from about 1% to about 99.9% by weight of the composition of the cleaning adjunct materials.
  • the compositions of the present invention preferably contain both a surfactant and a builder compound and additionally one or more cleaning adjunct materials preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Laundry compositions can also contain softening agents, as additional cleaning adjunct materials.
  • compositions of the present invention can also be used as detergent additive products in solid or liquid form.
  • Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the laundry process.
  • the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at 20°C.
  • the "compact" form of the laundry compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
  • the inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulfates and chlorides.
  • a preferred filler salt is sodium sulfate.
  • the major component of the liquid phase of the detergent compositions herein comprises one or more non-aqueous organic diluents.
  • the non-aqueous organic diluents used in this invention may be either surface active, i.e., surfactant, liquids or non- aqueous, non-surfactant liquids referred to herein as non-aqueous solvents.
  • the term "solvent” is used herein to connote the non-surfactant, non-aqueous liquid portion of the compositions herein. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvenf'-containing liquid phase, other components will be present as particulate material dispersed within the "solvenf'- containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • the non-aqueous liquid diluent component will generally comprise from about 50% to 100%), more preferably from about 50% to 80%>, most preferably from about 55% to 75%, of a structured, surfactant-containing liquid phase.
  • the liquid phase of the compositions herein, i.e., the non-aqueous liquid diluent component will comprise both non-aqueous liquid surfactants and non-surfactant non-aqueous solvents.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12 - C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated CQ-CU primary alcohol having about
  • Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of C ⁇ ⁇ to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Other types of alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14- 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
  • alcohol alkoxylate nonionic surfactant is utilized as part of the non-aqueous liquid phase in the detergent compositions herein, it will preferably be present to the extent of from about 1%> to 60%> of the composition structured liquid phase. More preferably, the alcohol alkoxylate component will comprise about 5%> to 40% of the structured liquid phase. Most preferably, an alcohol alkoxylate component will comprise from about 5% to 35% of the detergent composition structured liquid phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of from about 1% > to 60%> by weight, more preferably from about 2% to 40%> by weight, and most preferably from about 5% to 25%o by weight, of the composition.
  • hexylene glycol (4-methyl-2,4-pentanediol), 1,6- hexanediol, 1,3-butylene glycol and 1,4-butylene glycol.
  • Hexylene glycol is the most preferred.
  • the non-aqueous liquid phase of the detergent compositions of this invention is prepared by combining with the non-aqueous organic liquid diluents hereinbefore described a surfactant which is generally, but not necessarily, selected to add structure to the non-aqueous liquid phase of the detergent compositions herein.
  • Structuring surfactants can be of the anionic, nonionic, cationic, and/or amphoteric types.
  • Preferred structuring surfactants are the anionic surfactants such as the alkyl sulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzene sulfonates.
  • anionic surfactant material which may be optionally added to the detergent compositions herein as structurant comprises carboxylate-type anionics.
  • Carboxylate-type anionics include the CJ O-CI 8 alkyl alkoxy carboxylates (especially the
  • R is typically a linear Cg - C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C1 Q-14 alkyl, and M is alkali metal.
  • R is about C ⁇ 2 an d M is sodium.
  • Conventional secondary alkyl sulfates may also be utilized as a structuring anionic surfactant for the liquid phase of the compositions herein.
  • Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure:
  • alkyl sulfates will generally comprise from about 1% to 30%> by weight of the composition, more preferably from about 5% to 25% by weight of the composition.
  • Non-aqueous liquid detergent compositions containing alkyl sulfates, peroxygen bleaching agents, and bleach activators are described in greater detail in Kong- Chan et al.; WO 96/10073; Publiched April 4, 1996, which application is incorporated herein by reference.
  • Alkyl polyalkoxylate sulfates are also known as alkoxylated alkyl sulfates or alkyl ether sulfates. Such materials are those which correspond to the formula
  • R ⁇ is a Ci 0-C22 alkyl group, m is from 2 to 4, n is from about 1 to 15, and M is a salt-forming cation.
  • R ⁇ is a C ⁇ -Cjg alkyl, m is 2, n is from about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium.
  • R ⁇ is a C12-C16, m is 2, n is from about 1 to 6, and M is sodium.
  • Ammonium, alkylammonium and alkanolammonium counterions are preferably avoided when used in the compositions herein because of incompatibility with peroxygen bleaching agents.
  • alkyl polyalkoxylate sulfates can also generally comprise from about 1%) to 30%) by weight of the composition, more preferably from about 5%> to 25%> by weight of the composition.
  • Non-aqueous liquid detergent compositions containing alkyl polyalkoxylate sulfates, in combination with polyhydroxy fatty acid amides, are described in greater detail in boutique et al; PCT Application No. PCT/US96/04223, which application is incorporated herein by reference.
  • anionic surfactant for use as a structurant in the compositions herein comprises the linear alkyl benzene sulfonate (LAS) surfactants.
  • LAS surfactants can be formulated into a specific type of anionic surfactant-containing powder which is especially useful for incorporation into the non- aqueous liquid detergent compositions of the present invention.
  • Such a powder comprises two distinct phases. One of these phases is insoluble in the non-aqueous organic liquid diluents used in the compositions herein; the other phase is soluble in the non-aqueous organic liquids.
  • this preferred anionic surfactant- containing powder which can be dispersed in the non-aqueous liquid phase of the preferred compositions herein and which forms a network of aggregated small particles that allows the final product to stably suspend other solid particulate materials in the composition.
  • Such a preferred anionic surfactant-containing powder is formed by co-drying an aqueous slurry which essentially contains a) one of more alkali metal salts of Cjo-i ⁇ linear alkyl benzene sulfonic acids; and b) one or more non-surfactant diluent salts.
  • a slurry is dried to a solid material, generally in powder form, which comprises both the soluble and insoluble phases.
  • the linear alkyl benzene sulfonate (LAS) materials used to form the preferred anionic surfactant-containing powder are well known materials. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference.
  • the alkyl benzene surfactant anionic surfactants are generally used in the powder- forming slurry in an amount from about 20 to 70% by weight of the slurry, more preferably from about 20% to 60% by weight of the slurry.
  • the powder- forming slurry also contains a non-surfactant, organic or inorganic salt component that is co-dried with the LAS to form the two-phase anionic surfactant- containing powder.
  • a non-surfactant, organic or inorganic salt component that is co-dried with the LAS to form the two-phase anionic surfactant- containing powder.
  • Such salts can be any of the known sodium, potassium or magnesium halides, sulfates, citrates, carbonates, sulfates, borates, succinates, sulfo- succinates and the like.
  • Sodium sulfate which is generally a bi-product of LAS production, is the preferred non-surfactant diluent salt for use herein. Salts which function as hydrotropes such as sodium sulfo-succinate may also usefully be included.
  • the non-surfactant salts are generally used in the aqueous slurry, along with the LAS, in amounts ranging from about 1 to 50% by weight of the slurry, more preferably from about 5% to 40%) by weight of the slurry.
  • Salts that act as hydrotropes can preferably comprise up to about 3% by weight of the slurry.
  • the aqueous slurry containing the LAS and diluent salt components hereinbefore described can be dried to form the anionic surfactant-containing powder preferably added to the non-aqueous diluents in order to prepare a structured liquid phase within the compositions herein.
  • Any conventional drying technique e.g., spray drying, drum drying, etc., or combination of drying techniques, may be employed. Drying should take place until the residual water content of the solid material which forms is within the range of from about 0.5% to 4%o by weight, more preferably from about 1% to 3% by weight.
  • the anionic surfactant-containing powder produced by the drying operation constitutes two distinct phases, one of which is soluble in the inorganic liquid diluents used herein and one of which is insoluble in the diluents.
  • the insoluble phase in the anionic surfactant-containing powder generally comprises from about 10%) to 45% by weight of the powder, more preferably from about 15%> to 35% by weight of a powder.
  • the anionic surfactant-containing powder that results after drying can comprise from about 45% to 94%>, more preferably from about 60% to 94%>, by weight of the powder of alkyl benzene sulfonic acid salts. Such concentrations are generally sufficient to provide from about 0.5% to 60%, more preferably from about 15% to 60%, by weight of the total detergent composition that is eventually prepared, of the alkyl benzene sulfonic acid salts.
  • the anionic surfactant-containing powder itself can comprise from about 0.45%) to 45%) by weight of the total composition that is eventually prepared.
  • the anionic surfactant-containing powder will also generally contain from about 2% to 50%), more preferably from about 2% to 25% by weight of the powder of the non- surfactant salts.
  • the combined LAS/salt material can be converted to flakes or powder form by any known suitable milling or comminution process.
  • the particle size of this powder will range from 0.1 to 2000 microns, more preferably from about 0.1 to 1000 microns.
  • a structured, surfactant-containing liquid phase of the preferred detergent compositions herein can be prepared by combining the non-aqueous organic diluents hereinbefore described with the anionic surfactant-containing powder as hereinbefore described. Such combination results in the formation of a structured surfactant- containing liquid phase. Conditions for making this combination of preferred structured liquid phase components are described more fully hereinafter in the "Composition Preparation and Use" section. As previously noted, the formation of a structured, surfactant-containing liquid phase pe ⁇ nits the stable suspension of colored speckles and additional functional particulate solid materials within the preferred detergent compositions of this invention.
  • R ⁇ is a C6-C12 alkyl group
  • n is from about 2 to about 4
  • X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent
  • R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-0(R5)) wherein R5 is H or methyl.
  • Especially preferred amines based surfactants include the following:
  • the amine based surfactant is described by the formula:
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2- acyloxy-alkane- 1 -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefm sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Preferred alkyl sulfate surfactants are the non-ethoxylated C12-15 primary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F
  • Rl is a hydrocarbyl moiety having chainlength of from about 8 to about
  • the term "structured” indicates a heavy duty liquid composition having a liquid crystalline lamellar phase and an infinite shear viscosity ( ⁇ o) value between 0 and about 3,000cp (centipoise), a shear index (n) value of less than about 0.6, a consistency index value, K, of above about 1,000, and a viscosity ( ⁇ ) measured at 20 s ⁇ l of less than about 10,000cp, preferably less than about 5,000cp.
  • a “zero shear” viscosity is above about 100,000cp wherein “zero shear” is meant a shear rate of 0.001 s"l or less.
  • the yield value of the compositions herein, obtained by plotting viscosity versus stress, is larger than 0.2Pa.
  • compositions herein are clear or translucent, i.e. not opaque.
  • Detersive Amine - Suitable amine surfactants for use herein include detersive amines according to the formula:
  • R is selected from C4 to Cg alkylene
  • Ri is selected from Ci -C2 alkyl or C2-C3 hydroxyalkyl
  • A is:
  • ampholytic surfactants include C 2 -C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-Ci 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C1 8 betaines and sulfobetaines
  • AE alkyl ethoxylates
  • Cg-Ci 2 alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
  • C12-C1 8 betaines especially ethoxylates and mixed ethoxy/propoxy
  • polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
  • the surfactants can in general be in acid or salt, for example sodium, potassium, ammonium or substituted ammonium, form.
  • the biodegradably branched surfactants offer substantial improvements in cleaning performance and/or usefulness in cold water and/or resistance to water hardness and/or economy of utilization.
  • Such surfactants can, in general, belong to any known class of surfactants, e.g., anionic, nonionic, cationic, or zwitterionic.
  • the biodegradably branched surfactants are synthesized through processes of Procter & Gamble, Shell, and Sasol.
  • L and R is from 9 to 15, more preferably, 10 to 14) and further, wherein L has no substituents other than A, R 1 and R 2 ;
  • M is a cation or cation mixture (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably selected from H, Na, K and mixtures thereof, more preferably still, selected from H, Na, and mixtures thereof) having a valence q (typically from 1 to 2, preferably 1);
  • a and b are integers selected such that said compounds are electroneutral (a is typically from 1 to 2, preferably 1, b is 1);
  • R 1 is C ⁇ -C alkyl (preferably C ⁇ -C 2 alkyl, more preferably methyl);
  • R 2 is selected from H and C ⁇ -C 3 alkyl (preferably H and C ⁇ -C 2 alkyl, more preferably H and methyl, more preferably H and methyl provided that in at least about 0.5, more preferably 0.7, more preferably 0.9 to 1.0 mo
  • the peroxygen bleach component in the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%), preferably to about 10%, more preferably to about 8%, by weight of the composition.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4- nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate
  • Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • these chelating agents will generally comprise from about 0.1% to about 15%., more preferably from about 0.1 % to about 3.0% by weight of the detergent compositions herein.
  • Additional suitable dye transfer inhibiting agents include, but are not limited to, cross-linked polymers.
  • Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

La présente invention concerne des détergents lessiviels de qualité professionnelle sous forme aqueuse, non aqueuse, de gel liquide et/ou de poudre. Ces détergents incluent d'une part au moins un granulat d'enzymes comprenant au moins un composant réduisant la densité du granulat d'enzymes, et d'autre part au moins un autre enzyme. On peut également ajouter à l'ensemble au moins un autre agent lavant conventionnel.
EP00904654A 1999-02-02 2000-02-02 Granules d'enzymes basse densite et compositions en integrant Withdrawn EP1149145A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11842699P 1999-02-02 1999-02-02
US118426P 1999-02-02
PCT/US2000/002666 WO2000046332A1 (fr) 1999-02-02 2000-02-02 Granules d'enzymes basse densite et compositions en integrant

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EP1149145A1 true EP1149145A1 (fr) 2001-10-31

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EP (1) EP1149145A1 (fr)
JP (1) JP2002535980A (fr)
CN (1) CN1343247A (fr)
AU (1) AU2638000A (fr)
BR (1) BR0007954A (fr)
CA (1) CA2360657A1 (fr)
WO (1) WO2000046332A1 (fr)

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JP7335362B2 (ja) 2019-06-12 2023-08-29 ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ 過酸化ジアシルを生成するためのプロセス
US11976035B2 (en) 2019-06-12 2024-05-07 Nouryon Chemicals International B.V. Process for the production of diacyl peroxides
US20220306490A1 (en) * 2019-06-12 2022-09-29 Nouryon Chemicals International B.V. Method for isolating carboxylic acid from an aqueous side stream

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000029534A1 (fr) * 1998-11-13 2000-05-25 Genencor International, Inc. Granule de faible densite sur lit fluidise
WO2000040689A2 (fr) * 1999-01-08 2000-07-13 Genencor International, Inc. Compositions de faible densite et matieres particulaires comprenant lesdites compositions

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
US4252664A (en) * 1978-10-30 1981-02-24 Colgate-Palmolive Company Effervescent granules
GB2168377A (en) * 1984-12-17 1986-06-18 Procter & Gamble Stable liquid dishwashing detergent containing abrasive, clay and low density particles
US4931195A (en) * 1987-07-15 1990-06-05 Colgate-Palmolive Company Low viscosity stable non-aqueous suspension containing organophilic clay and low density filler

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000029534A1 (fr) * 1998-11-13 2000-05-25 Genencor International, Inc. Granule de faible densite sur lit fluidise
WO2000040689A2 (fr) * 1999-01-08 2000-07-13 Genencor International, Inc. Compositions de faible densite et matieres particulaires comprenant lesdites compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.F.G.HARRIS, A. M. HILDON: "Reducing Segregation in Binary Powder Mixtures with Particular Reference to Oxygenated Washing Powders", IND. ENG. CHEM. PROCESS DES. DEVELOP., vol. 9, no. 3, pages 363 - 367 *
See also references of WO0046332A1 *

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AU2638000A (en) 2000-08-25
WO2000046332A1 (fr) 2000-08-10
CN1343247A (zh) 2002-04-03
BR0007954A (pt) 2001-11-06
CA2360657A1 (fr) 2000-08-10
JP2002535980A (ja) 2002-10-29

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