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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
• • 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
  • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
• • 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
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

• the present invention is related to granular detergent compositions which are useful for cleaning and softening of fabrics, and for giving other fabric-care benefits such as appearance improvements and rejuvenation.
• compositions herein contain a fabric-softening clay material, and a cellulase enzyme, which is in the form of granulates containing calcium carbonate.
• detergent compositions are the ones which have been disclosed in British patent 1,514,275 - 1,400,898, or EPA 0 026 528.
• Cellulase enzymes have already been used in detergent compositions for their cleaning abilities, as disclosed in British Patent Application GB-A 2,095,275, GB-A-2,094,826, or Japanese patent 57108-199.
• EP-A 0 120 528 teaches alkaline softening detergent compositions comprising a synergistic mixture of a water-insoluble C10-C26 tertiary amine and cellulase.
• EP-A 0 177 165 discloses alkaline softening detergent compositions containing a mixture of smectite clay and cellulase.
• EP-A 0 220 016 discloses the fabric color-clarification effect derivable from the use of cellulase in a detergent context.
• the cellulase enzymes are usually incorporated in the composition in the form of granulates, also identified as marumes, or prills, which are supplied by the enzyme manufacturer.
• Such granulates are disclosed in e.g. EP-A-170 360 and U.S.-A-4,435,307, which mention certain ingredients which need to be incorporated to the granulates during their making, for e.g. non-dusting and color purposes.
• Calcium-carbonate has been disclosed as colorant for laundry detergent enzyme granulates in GB-A-2,167,758 and in Japan Kokai JP 61,107,935.
• the present invention relates to granular detergent compositions containing a fabric-softening clay material, and cellulase granulates containing from 1% to 50%, by weight, preferably 5% to 15% of the granulates, of calcium carbonate.
• Calcium carbonate is preferably coated onto the cellulase granulates.
• the invention also relates to the above-described cellulase granulates per-sé.
• compositions herein are capable of cleaning and softening the treated fabrics, as well as giving benefits in terms of fabric appearance improvements and rejuvenation.
• the cellulase usable in the present invention may be any bacterial or fungal cellulase having an optimum pH of between 5 and 9.5.
• Suitable cellulase are disclosed in U.S.-A-4,435,307, GB-A-2.095.275, DE-OS-2.247.832, and EP-A 0 220 016.
• cellulases examples include cellulases produced by a strain of Humicola Insolens (Humicola grisea var. thermoidea), particularly by the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
• One CMCase unit is defined as the amount of enzyme which forms per minute an amount of reducing carbohydrate equivalent to 10 ⁇ 6 mole of glucose, in the above-described conditions.
• a useful range of cellulase activity in the present context is from 5 to 1360, preferably from 60 to 140 CMCase activity units/gram of detergent composition.
• Cellulase enzymes for use in granular detergent compositions are typically supplied in the form of granulates, e.g. marumes or prills.
• Such granulates contain a majority of crude cellulase enzyme, together with additional ingredients, such as polyethylene glycol, at typical levels of from 5 % to 7 %, and cellulose at typical levels of but 10%.
• additional ingredients such as polyethylene glycol, at typical levels of from 5 % to 7 %, and cellulose at typical levels of but 10%.
• the polyethylene glycol for use herein can have a molecular weight in the range from 500 to 8000.
• the amount of cellulase in the granules is determined by the total cellulase activity of the composition, which has to be in the limits set up hereinabove.
• compositions of the invention should, therefore, preferably be free of titanium dioxide and magnesium silicate.
• the calcium carbonate is present in the cellulase granulates, at levels of from 1% to 50%, preferably 5% to 15% by weight, of the granulates.
• Calcium carbonates of a particle size range from 1 to 10 ⁇ m have been found to be particularly suitable for the purpose of the present invention.
• the calcium carbonate used herein may be used as is or in coated form, typically coated with stearic acid.
• calcium carbonate either as is or already coated with e.g. stearic acid, is coated onto the cellulase granulates.
• Cellulase granulates can be prepared in a number of different ways, for example by means of a "Marumerizer” as described in Britisch Pat.Nos. 1,362,365 and 1,361,387 or by means of a granulating machine, as described in Auftungs-Technik No. 3/1970, pp. 147-153 and No. 5/1970, pp. 262-278, or can be prilled granulates as described in Belgian Patent Specification No. 760.135. In all cases, the granulates must have low dusting properties.
• the calcium carbonate herein is either mixed with the other ingredients during the making of the granulates, or mixed with cellulase before granulation, or, preferably, coated onto the granulates which have been prepared as described hereinabove, by conventional coating methods.
• the cellulase granulates according to the present invention are present at levels of from 1 % to 50 % by weight of the detergent composition herein, preferably 1.5 % to 10 % by weight.
• the surface-active agent is the surface-active agent
• the surface active agent useful herein may be selected from anionic, nonionic, zwitterionic surfactants and is present at levels of from 1 % to 50 % by weight of the composition, preferably from 10 % to 30 %.
• Suitable anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acyloxy-alkane-1-sulphonates, and beta-alkyloxy alkane sulphonates.
• Especially preferred alkyl benzene sulphonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, especially from 11 to 13 carbon atoms.
• Suitable alkyl sulphates have from 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms.
• Suitable alkyl polyethoxy ether sulphates have from 10 to 18 carbon atoms in the alkyl chain and have an average of from 1 to 12 - CH2CH2O- groups per molecule, especially from 10 to 16 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2CH2O-groups per molecule.
• Suitable paraffin sulphonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms.
• Suitable alpha-olefin sulphonates have from 10 to 24 carbon atoms, more especially from 14 to 16 carbon atoms; alpha-olefin sulphonates can be made by reaction with sulphur trioxide, followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulphonates.
• Suitable alpha-sulphocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alpha-sulphonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.
• Suitable alkyl glyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow.
• Suitable alkyl phenol polyethoxy ether sulphates have from 8 to 12 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2CH2O-groups per molecule.
• Suitable 2-acyloxyalkane-1-sulphonates contain from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety.
• Suitable beta-alkyloxy alkane sulphonates contain from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
• the alkyl chains of the foregoing anionic surfactants can be derived from natural sources such as coconut oil to tallow, or can be made synthetically as for example by using the Ziegler or Oxo processes. Water-solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulphonate having 11-13 carbon atoms in the alkyl group and alkyl sulphate having 12 to 18 carbon atoms in the alkyl group.
• Suitable nonionic surfactants to be incorporated in the compositions herein are water-soluble ethoxylated materials of HLB 11.5-17.0 and include (but are not limited to) C10-C20 primary and secondary alcohol ethoxylates and C6-C10 alkylphenol ethoxylates.
• C14-C18 linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, examples being C14-C15 (EO)7, C16-C18 (EO)25 and especially C16-C18 (EO)11.
• Cationic co-surfactants which can be used herein, include water-soluble quaternay ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R7 are each C1to C7 alkyl, preferably methyl; X ⁇ is an anion, e.g. chloride.
• Examples of such trimethyl ammonium compound include C12-C14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.
• compositions of the invention should be essentially free of water-insoluble long-chain alkyl amine softening agents, and derivatives thereof, since it has been discovered that they interact negatively with cellulase, in the pH conditions of the present invention.
• Derivatives of the amine softening agents include the corresponding amine compounds.
• Such amine softening agents are disclosed in e.g. EP.A. 0.026.528 and EP.A 0.120.528. and include in particular amines of the formula R1R2R3N where R1 and R2 are C6 to C20 alkyl chains, and R3 is C1 to C10 alkyl chain or hydrogen.
• composition herein should be formulated at a pH in the range of from 6.5 to 9.5, measured as a 1 % solution of the composition in distilled water. At this pH-range, the cellulase for use herein have their optimum performance.
• compositions herein must contain a clay softening agent.
• clay softening agents are well-known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included among such clay softeners are various heat-treated kaolins and various multi-layer smectites. Preferred clay softeners are smectite softener clays that are described in German patent document 23 34 899 and in U.K. patent 1,400,898.
• the most preferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarily montmorillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material.
• Softener clays are used in the compositions at levels of 1-20 %, preferably 2-10 % by weight of the composition.
• compositions herein may contain, in addition to the essential ingredients, certain optional ingredients.
• through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant.
• detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, and mixtures thereof.
• Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here.
• U.S. Patent 3.579.454 contains typical examples of the use of such materials in various cleaning compositions.
• Preferred polyfunctional organic acids species for use herein are citric acid, ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid.
• a further class of detergency builder materials useful in the present invention are insoluble sodium alumino-silicates.
• the 1-10 ⁇ m size zeolite (e.g., zeolite A) builders disclosed in German patent 24.22.655 are especially preferred for use in low-phosphate or non-phosphate compositions.
• the builder/sequestrant will comprise from 0.5 % to 45 % of the composition.
• compositions herein can also contain fatty acids, saturated or unsaturated, and the corresponding soaps.
• fatty acids, saturated or unsaturated have from 10 to 18 carbon atoms in the alkyl chain.
• unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid.
• the corresponding soaps can also be used.
• the optional fatty acid/soaps are used in levels up to 20 %.
• compositions herein can also contain compounds of the general formula R-CH(COOH)CH2(COOH), i.e. derivatives of succinic acid, wherein R is C10-C20 alkyl or alkenyl, preferably C12-C16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.
• the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
• succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred) and 2-pentadecenyl succinate.
• Also useful as builders in the present context are the compounds described in U.S. patent 4.663.071, i.e. mixtures of tartrate monosuccinic acid and tartrate disuccinic acid in a weight ratio of monosuccinic to disuccinic of from 97:3 to 20:80, preferably 95:5 to 40:60.
• bleaching agent Another optional ingredient is a bleaching agent.
• peroxygen bleaching agents such as sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.
• Bleach activators may be used in combination with the above peroxygen bleaching agents.
• Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates.
• preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-octanoyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate ; bisphenol diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
• peroxygen bleach activators which are disclosed in U.S. Patents 4,483,778 and 4,539,130, are alpha-substituted alkyl or alkenyl esters, such as sodium-4(2-chlorooctanoyloxy)benzene sulfonate, sodium 4-(3,5, 5-trimethyl hexanoyloxy)benzene sulfonate.
• Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application 0 166 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxycarbyl group, X is a heteroatom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
• Enzymes other than cellulases such as proteolytic, amylolytic, or lipolytic enzymes can be used in addition to the cellulase herein.
• Soil-release/soil-suspending agents can be present in the composition herein at levels typically from 0.1 % to 10 % by weight.
• alkoxylated polyamines suitable as clay-soil removal/anti-redeposition agents can be used.
• polyamines as used herein represents generically the alkoxylated polyamines, both in their amine form and in their quaternized form.
• Such materials can conventiently be represented as molecules of the empirical structures with repeating units: wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C1 ⁇ C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably 10-20; n is an integer of at least 2, preferably 2-20, most preferably 3-5; and X ⁇ is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
• polyamines for use herein are the so-called ethoxylated polyethylene imines, i.e., the polymerized reaction product of ethylene oxide with ethyline-imine, having the general formula : wherein n in an integer of 3 to 5 and y is an integer of 10 to 20.
• Soil suspending agents can also be selected from polyethylene glycols, of molecular weight 400 to 1000, polyacrylates, or copolymers of acrylic acid and maleic anhydride/acid.
• the detergent compositions herein are preferably free of carboxymethylcellulose.
• compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
• Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach stabilizing agents.
• a granular detergent composition was prepared, according to the following table :
• composition A to be used as reference, where cellulase granulates (1.79 % by weight of total composition) containing crude cellulase enzymes and cellulose, were dry-mixed with the rest of the composition.
• Composition B a composition according to the present invention, where cellulase granulates (1.79 % by weight of total composition) containing crude cellulase enzyme, cellulose, and a coating of polyethylene glycol (5 % weight level of granulates, MW 1500) and of calcium carbonate (10 % weight level of granulates).
• the cellulase was of the type described in U.S.-A-4,435,307 and its amounts were such as to give an activity of 68 CMCase activity units/g of composition.
• compositions A and B were compared for softness and fabric-care performance.
• the design of the test was such as to compare softness of textile pieces laundered 4, 8 and 12 times (multi-cycle) each time with invention and reference composition.
• the testing conditions were as follows :

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• 1987
  • 1987-11-19 GB GB878727081A patent/GB8727081D0/en active Pending
• 1988
  • 1988-11-17 IN IN1001DE1988 patent/IN183413B/en unknown
  • 1988-11-18 WO PCT/DK1988/000189 patent/WO1989004862A1/en active IP Right Grant
  • 1988-11-18 AT AT89900022T patent/ATE84818T1/de not_active IP Right Cessation
  • 1988-11-18 CA CA000583568A patent/CA1336894C/en not_active Expired - Fee Related
  • 1988-11-18 JP JP1500029A patent/JP2735663B2/ja not_active Expired - Lifetime
  • 1988-11-18 EP EP89900022A patent/EP0383828B1/en not_active Expired - Lifetime
  • 1988-11-18 KR KR1019890701353A patent/KR950013920B1/ko not_active IP Right Cessation
  • 1988-11-18 IE IE346588A patent/IE61734B1/en not_active IP Right Cessation
  • 1988-11-18 BR BR888807805A patent/BR8807805A/pt not_active IP Right Cessation
  • 1988-11-18 AU AU26117/88A patent/AU634705B2/en not_active Ceased
  • 1988-11-18 DE DE8989900022T patent/DE3877768T2/de not_active Expired - Fee Related
  • 1988-11-19 MY MYPI88001320A patent/MY103481A/en unknown
  • 1988-11-19 CN CN88108833A patent/CN1026124C/zh not_active Expired - Fee Related
  • 1988-11-21 NZ NZ227025A patent/NZ227025A/en unknown
  • 1988-11-21 MX MX013871A patent/MX169695B/es unknown
• 1990
  • 1990-05-04 DK DK110890A patent/DK164708C/da not_active IP Right Cessation
  • 1990-05-17 FI FI902446A patent/FI92496C/fi not_active IP Right Cessation
• 1994
  • 1994-01-07 CN CN94100297A patent/CN1092101A/zh active Pending
• 1996
  • 1996-08-01 HK HK143896A patent/HK143896A/xx not_active IP Right Cessation

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