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WO1993021294A1 - Utilisation de polyesters modifies pour le lavage de textiles contenant du coton - Google Patents

Utilisation de polyesters modifies pour le lavage de textiles contenant du coton Download PDF

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Publication number
WO1993021294A1
WO1993021294A1 PCT/US1993/003245 US9303245W WO9321294A1 WO 1993021294 A1 WO1993021294 A1 WO 1993021294A1 US 9303245 W US9303245 W US 9303245W WO 9321294 A1 WO9321294 A1 WO 9321294A1
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WO
WIPO (PCT)
Prior art keywords
weight
polyester
composition
acid
fabrics
Prior art date
Application number
PCT/US1993/003245
Other languages
English (en)
Inventor
Robin Gibson Hall
Timothy Williams
Olivier Houpert
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP93912134A priority Critical patent/EP0641378A4/fr
Priority to CA002117997A priority patent/CA2117997A1/fr
Priority to JP5518439A priority patent/JPH07505670A/ja
Priority to BR9306245A priority patent/BR9306245A/pt
Publication of WO1993021294A1 publication Critical patent/WO1993021294A1/fr
Priority to KR1019940703635A priority patent/KR950700976A/ko

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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • 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
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/07—Cellulose esters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15—Proteins or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms

Definitions

  • the present invention relates to the use of modified polymers known for their soil-release properties, as cleaning agents for cotton-containing fabrics; the invention further relates to certain detergent compositions containing said modified polymers.
  • Products used in laundering operation contain a number cr ingredients which provide certain basic benefits.
  • laundry cleaning products are formulated with detergent surfactant systems to remove a variety of soils from clothes during washing.
  • These laundry products can also include ingredients which provide through-the-wash fabric conditioning benefits such as softening and anti-static performance.
  • laundry detergent can also impart other desirable properties.
  • the hydrophobic character of polyester fabrics makes their laundering difficult, particularly as regards oily soil and oily stains.
  • the oily soil or stain preferentially "wets" the fabric. As a result, the oily soil or stain is difficult to remove in an aqueous laundering process.
  • polyesters have been found to be particularly useful as soil release compounds in laundry detergent composition. During the laundering operation, these soil release polyesters adsorb onto the surface of fabrics immersed in the wash solution. The adsorbed polyesters then form a hydrophilic film which remains on the fabric after it is removed from the wash solution and dried. This film can be renewed by subsequent washing of the fabric with a detergent composition containing the soil release polyesters.
  • polyesters are disclosed in e.g. US Patent 4 116 885 and 4 711730.
  • the present invention is based on the discovery that the selected modified polyesters herein can act in a "surfactant" mode versus cotton-containing fabrics, thus being able to provide a cleaning effect on such fabrics after only one laundering cycle, as compared to several cycles when functioning in the soil-release agent mode.
  • the modified polyesters herein are random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target being to obtain is a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • the cellulase usable in the combination with the modified polyesters herein may be any bacterial or fungal cellulase, having a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in GB-A-2 075 028; GB-A-2 095275 and DE-OS-24 47 832.
  • cellulases examples include cellulase produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly by the Humicola strain DSM 1800, and cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mullosc (Dolabella Auricula Solander).
  • the cellulase added to the composition of the invention may be in the form of a non-dusting granulate, e.g. "marumes” or “prills”, or in the form of a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.
  • a non-dusting granulate e.g. "marumes” or "prills”
  • a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.
  • Preferred cellulases for use herein are characterized in that said cellulase they provide at least 10% removal of immobilized radioactive labelled carboxymethy1-cellulose according to the C14CMC-method described in EPA 35O 098 at 25 ⁇ l0 -6 % by weight of cellulase protein in the laundry test solution.
  • a cellulase preparation useful in the compositions of the invention can consist essentially of a homogeneous endoglucanase component, which is immunoreactive with an antibody raised against a highly purified 43kD cellulase derived from Humicola insolens. DSM 1800, or which is homologous to said 43kD endoglucanase.
  • the modified polyesters herein typically achieve their cleaning benefits on cotton-containing fabrics by being incorporated into a detergent composition including other detersive ingredients, at a level of from 0.025% to 10% by weight of the composition.
  • the modified polyester herein can be added separately, to the laundry cycle, in the form of a detergent additive; said additive posssibly containing other selected detergent active materials, such as soil anti-redeposition agents and co-dispersing agents, and/or cellulase enzyme; in particular, the modified polyesters herein can be used to pretreat cotton-containing fabrics, before the main wash cycle of 3 laundering processs.
  • the detergent compositions herein can be in a liquid or granular form and are preferably delivered directly to the drum and not indirectly and via the outer casing of the machine This can most easily be achieved by incorporation of the composition in a bag or container from which it can be released at the start of the wash cycle in response to agitation, a rise in temperature or immersion in the wash water in the drum. Such a container will be placed in the drum, together with the fabrics to be washed. Alternatively the washing machine itself may be adapted to permit direct addition of the composition to the drum e.g. by a dispensing arrangement in the access door.
  • a rigid container such as disclosed in EPA 151 549 can be used the detergent composition herein are preferably in granular form, and the container will be flexible, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in EPA no. 0 018 678.
  • it may be formed of a water insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in EPAs nos. 0 Oil 500, 0 Oil 501, 0 Oil 502, and 0 Oil 968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • laminated sheet products can be employed in which a central flexible layer is impregnated and/or coated with a composition and then one or more outer layers are applied to produce a fabric-like aesthetic effect.
  • the layers may be sealed together so as to remain attached during: use or may separate on contact with water to facilitate the release of the coated or impregnated material.
  • An alternative laminate form comprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the detergent components are deposited in measured amounts, with a second layer overlying the first layer and sealted thereto in those areas between the pouch-like containers where the two layers are in contact.
  • the components may be deposited in particulate, paste or molten form and the laminate layers should prevent egress of the contents of the pouch-like containers prior to their addition to water.
  • the layers may separate or may remain attached together on contact with water, the only requirement being that the structure should permit rapid release of the contents of the pouch-like containers into solution.
  • the number of pouch-like containers per unit area of substrata is a matter of choice but will normally vary between 500 and 25,000 per square meter.
  • Suitable materials which can be used for the flexible laminate layers in this aspect of the invention include, among others, sponges, paper and woven and non-woven fabrics.
  • the preferred means of carrying out the washing process according to the present invention includes the use of a reusable dispensing device having walls that are permeable to liquid but impermeable to the solid composition.
  • Devices of this kind are disclosed in EPAs Nos. 0 343 069 and 0 344 070.
  • the latter Application discloses a device comprising a flexible sheet in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing cycle. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium.
  • the support ring is provided with a masking arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spooked wheel configuration, or a similar structure in which the walls have a helical form.
  • the detergent compositions herein contain a surfactant.
  • a wide range of surfactants can be used in the detergent compositions.
  • anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulfate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C 18 fatty source preferably from a C 16 -C 18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulfate surfactants are alkyl sulfates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulfates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • alkyl sulfates herein are tallow alkyl sulfate, coconut alkyl sulfate, and C 14-15 alkyl sulfates.
  • the cation in each instance is again an alkali metal cation, preferably sodium.
  • One class of nonionic surfactants particularly useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 5 to 17, preferably from 6 to 14, more preferably from 7 to 12.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 14 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol, the C 12 -C 15 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol, and mixtures thereof.
  • Another suitable class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • RO C n H 2n O
  • t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-3 0 070 077, 0 075 996 and 0 094 113.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
  • R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C 8 -C 20, preferably C 10 -C 14 N-alkyl or alkenyl amine oxides and propylene-l,3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • amphoteric surfactants such as polyamine-based species.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C 8 -C 16 , preferably C 10 -C 14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the detergent compositions can comprise from 1%-70% by weight of surfactant, but usually the surfactant is present in the compositions herein an amount of tro ⁇ 1% to 30%, more preferably from 10-25% by weight.
  • the detergent compositions herein also contain a builder
  • Builder materials will typically be present at from 5% to 80% of the detergent compositions herein.
  • the compositions herei are free or substantially free of phosphate-containing builders (substantially free being herein defined to constitute less than 1% of the total detergent builder system), and the builder system herein consists of water-soluble builders, waterinsoluble builders, or mixtures thereof.
  • Water insoluble builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated Zeolite A, X, B or HS.
  • Preferred aluminosilicate ion-exchange materials have the unit cell formula
  • M is a calcium-exchange cation
  • z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate materials are in hydrated form and are preferably crystalline containing from 10% to 28%, more preferably from 18% to 22% water.
  • aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example microscopic determination utilizing a scanning electron microscope.
  • the aluminosilicate ion exchange materials are further characterized by their calcium ion exchange capacity which is at least 200 mg equivalent of CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is described in detail in GB-1 429 143.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula
  • x is from 20 to 30, especially 27.
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O5).
  • the high Ca ++ /Mg ++ binding capacity is mainly a cation exchange mechanism. In hot water, the material becomes more soluble.
  • the water-soluble builder can be a monomeric or oligomeric carboxylate chelating agent.
  • Suitable carboxylates containing one carboxy group include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 368, 821 369 and 821 370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, :naleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2 446 686, and 2 446 687 and U.S. Patent No. 3 935 257 and the sulfinyl carboxylates described in Belgian Patent No. 840623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyl ⁇ xysuccinates described in British Patent 1 379 241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1, 3-propane tricarboxylates described in British Patent No. l 387 447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 261 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 398 421 and 1 398 422 and in U.S. Patent No. 3 936 448, and the sulfonated pyrolysed citrates described in British Patent No. 1 082 179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1 439 000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cistetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1 425 343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the preferred granular detergent compositions herein include a mixture of a water- insoluble aluminosilicate builder such as zeolite A, and a water-soluble carboxylate chelating agent such as citric acid.
  • builder materials that can form part of the builder system for the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
  • the detergent compositions herein will contain a cellulase enzyme such as described above, at levels of from 0.025% to 10% of the composition.
  • the detergent compositions or detergent additives herein will contain a soil anti redeposition or soil suspension agent, in combination with the modified polyesters herein.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, homo- or copolymeric polycarboxylic acids or their salts and polyaminoacid coumpounds.
  • Polymers of this type include the polyaerylates and maleic anhydride-acrylic acid copolymers disclosed in detail in EPA 137 669, as well as copolymers of maleic anydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer.
  • Polyaminoacid compounds such as those derived from aspartic acid are for instance disclosed in British patent application No. 9226942.2.
  • compositions herein are normally used at levels of from 0.025% to 5% by weight, of the compositions herein.
  • the present detergent compositions are preferably in granular form and more preferably in a "compact" form, i.e. having a density, which is higher than the density of conventional detergent compositions.
  • the preferred density of the compositions herein ranges from 550 to 950g/liter, preferably 650 to 850g/liter of composition, measured at 20°C.
  • the present "compact" form of the most preferred compositions herein is best reflected, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder for, in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition.
  • 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.
  • Inorganic filler salts such as meant in the present compositions are selected from the alkali and alkaline-earthmetal salts of sulfates and chlorides.
  • a preferred filler salt is sodium sulfate.
  • compositions will typically include optional ingredients that normally form part of detergent compositions.
  • Enzymes, optical brighteners, bleaches, bleach activators, suds suppressors, anticacking agents, dyes and pigments are examples of such optional ingredients and can be added in varying amounts as desired.
  • Enzymes such as proteases, lipases, or amylases are particularly desirable ingredients of the compositions herein.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,4 1 -bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2 1 disulphonate, disodium 4, - 4 1 -bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2 1 - disulphonate, disodium 4,4 1
  • any particulate inorganic perhydrate bleach can be used, in an amount of from 3% to 40% by weight, more preferably from 8% to 25% by weight and most preferably from 12% to 20% by weight of the compositions.
  • Preferred examples of such bleaches are sodium perborate monohydrate and tetrahydrate, percarbonate, and mixtures thereof.
  • Another preferred separately mixed ingredient is a peroxy carboxylic acid bleach percursor, commonly referred to as a bleach activator, which is preferably added in a prilled or agglomerated form in granular detergents.
  • a bleach activator a peroxy carboxylic acid bleach percursor
  • suitable compounds of this type are disclosed in British Patent Nos. 1586769 and 2143231 and a method for their formation into 3 prilled form is described in European Published Patent Application No. 0 062 523.
  • Preferred examples of such compounds are tetracetyl ethylene diamine and sodium 3, 5, 5 trimethvl hexanoyloxybenzene sulphonate.
  • Bleach activators are normally employed at levels of from 0.5% to 10% by weight, more frequently from 1% to 8% and preferably from 2% to 6% by weight of the composition.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water- dispersible substantially non-surface-active detergent impermeable carrier Alternatively the suds suppressor can be dissolved cr disperse in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 millimicrons to 20 millimicrons and a specific surface area above 50 m 2 /g intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200 000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially availably from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • the incorporation of the suds mofidiers is preferably made as separate particulates, and this permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MW copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al U.S. Patent No. 3 933 672.
  • Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays aiscioseo in GB-A-1 400 898. Organic fabric softening agents include the water-soluble tertiary amines as disclosed in GB-A-1 400 898.
  • Organic fabric softening agents include the water-insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B-O Oil 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-O 026 527 and EP-B-O 026 528 and di-long-chain amides as disclosed in EP-B-O 242 919.
  • Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-O 299 575 and 0 313 146.
  • levels of smectite clay are normally in the range from 5% to 20%, more preferably from 8% to 15% by weight with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the waterinsoluble tertiary amines or di-long-chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water-soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.
  • compositions herein may also contain dye-transfer inhibiting agents such as polyvinylpyrrolidones having a molecular weight from 5 000 to 2 200, typically present in the preferred granular detergent compositions herein, at level such as to deliver from 5 to 500 mg/1 of said polyvinyl pyrrolidones in the wash solution.
  • dye-transfer inhibiting agents such as polyvinylpyrrolidones having a molecular weight from 5 000 to 2 200, typically present in the preferred granular detergent compositions herein, at level such as to deliver from 5 to 500 mg/1 of said polyvinyl pyrrolidones in the wash solution.
  • TAS sodium salt of tallow alcohol sulfate
  • FA45E7 fatty alcohol (C14-C15) ethoxylated with about 7
  • FA25E3 fatty alcohol (C12-15) ethoxylated with about 3
  • Zeolite A4 sodium salt of zeolite 4A with average particle size between 1 - 10 micrometer
  • Copolymer AA/MA copolymer of acrylic acid and maleic acid
  • PAA Polyacrylate polymer
  • Phosphonate sodium salt of ethylenediamine tetramethylene
  • EDTA sodium salt of ethylenediamine tetra acetate
  • TAED tetra acetyl ethylene diamine
  • PVP Polyvinylpyrrolidone
  • Amylase Termamyl 60T (Novo-Nordisk)
  • Lipase Lipolase 100T (Novo-Nordisk)
  • the process of preparation of the selected polyester hereir. includes mixing all the monomers in a round bottomed flas ⁇ , stirring at 180oC, until a clear solution results, and continue stirring for 24 hours. Then transferring the contents of the round bottomed flask to further singie necked round bottomed flask (typically 1 litre), heating under vacuum for 45 minutes at 200°C, removing from flask and cooling. A clear glass solid is obtained, which is then crushed gently to be used.
  • a bundle of soiled fabrics containing fabrics which were stained with a range of stains such as particulate soils, greasy soilss, enzymatic soils and bleachable soils on cotton and p ⁇ lycotton fabrics were washed in a compact detergent with the formulation as shown.
  • One half of each bundle was washed with detergent composition as shown and the other half was washed with the same composition without the cellulase.
  • the testing was carried out at 40°C in water of 25oH (German hardness). All testing was repeated 4 times.
  • Stain removal was evaluated relative to a reference stain each type previously washed under identical conditions.
  • the formulation used for the wasning of the reference fabri contained no modified ooivester cr DCiuiase.
  • Stain removal was evaluated using the well known schefe scale of panel score units determined by two judges as follows :
  • a detergent of formulation similar to that described in example 1 was used to wash a bundle of soiled fabrics which were stained with a range of soils of particuiate, greasy, enzymatic and bleachable types.
  • One half of each bundle was washed in the formulation described in example 1, the other half of the bundle was washed in the identical formula without modified polyester.
  • the conditions used fcr washing these bundles were 40°C and 25 H water. 4 replicates of each test were carried out and the samples were graded accordingly to the % stain removal. This was calculated using the McBeth (colour spectrometer) using the conventional l a b system. The tests were repeated using different levels of modified polyesters between 0.025% and 10% by weight of the detergent composition.
  • Typical greasy stains considered include dirty motor oil, shoe polish and make up.
  • Polycotton swatches were pretreated a number of times with a detersive formulation containing the carboxy methyl cellulose (CMC) .
  • CMC carboxy methyl cellulose
  • the purpose of this was to give the fabric a history of CMC deposition onto the cotton of the polycotton.
  • the polycotton was then dryed and stained with dirty motor oil (DMO) .
  • DMO dirty motor oil
  • One half of the stains was washed in a detersive formulation similar to that described in example one to act as a reference whilst the other half was washed in the same formulation only containing the modified polyester herein.
  • the swatches were graded by calculating the % stain removal from each tracer using the hunter colour lab system. All data was also compared to swatches which had been treated in exactly the same way as described above only with a detersive formulation containing soil release polymer and no CMC. The results are described below.
  • Zeolite 4A 32.00 15.00 16.00 20.00 15.00 13.00 13.00
  • Copolymer AA/MA 4.10 5.00 3.50 3.50 ⁇ 5.00. 3.00

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Textile Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention se rapporte à l'utilisation de polyesters modifiés sélectionnés, connus pour leurs propriétés anti-salissantes en tant qu'agents de lavage pour les textiles contenant du coton. Lesdits polyesters sont capables de produire un effet nettoyant sur ces textiles après seulement un cycle de lavage alors que plusieurs cycles sont nécessaires avec un agent anti-salissure classique. L'invention concerne également des compositions détergentes contenant lesdits polyesters modifiés et une cellulase, ou un agent de co-dispersion et/ou un agent d'antiredéposition.
PCT/US1993/003245 1992-04-13 1993-04-07 Utilisation de polyesters modifies pour le lavage de textiles contenant du coton WO1993021294A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP93912134A EP0641378A4 (fr) 1992-04-13 1993-04-07 Utilisation de polyesters modifies pour le lavage de textiles contenant du coton.
CA002117997A CA2117997A1 (fr) 1992-04-13 1993-04-07 Utilisation de polyesters modifies pour le lavage des tissus contenant du coton
JP5518439A JPH07505670A (ja) 1992-04-13 1993-04-07 綿含有布帛の洗浄用変性ポリエステルの用途
BR9306245A BR9306245A (pt) 1992-04-13 1993-04-07 Uso de poliésteres modificados para a lavagem de tecidos contendo algodao
KR1019940703635A KR950700976A (ko) 1992-04-13 1994-10-13 면-함유 직물의 세탁을 위한 개질된 폴리에스테르의 용도(Use of modified polyesters for the washing of cotton-containing fabrics)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP92870060.8 1992-04-13
EP92870060 1992-04-13
EP92202383 1992-07-31
EP92202383.3 1992-07-31

Publications (1)

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WO1993021294A1 true WO1993021294A1 (fr) 1993-10-28

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EP (1) EP0641378A4 (fr)
JP (1) JPH07505670A (fr)
KR (1) KR950700976A (fr)
CN (1) CN1078747A (fr)
AU (1) AU4279393A (fr)
BR (1) BR9306245A (fr)
CA (1) CA2117997A1 (fr)
CZ (1) CZ248694A3 (fr)
EG (1) EG20531A (fr)
HU (1) HUT69329A (fr)
IE (1) IE930280A1 (fr)
MA (1) MA22870A1 (fr)
MX (1) MX9302143A (fr)
WO (1) WO1993021294A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996008554A1 (fr) * 1994-09-16 1996-03-21 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de blanchiment en poudre contenant des enzymes
WO1997019161A1 (fr) * 1995-11-20 1997-05-29 Henkel Kommanditgesellschaft Auf Aktien Preparation enzymatique contenant un polymere facilitant le lavage
WO1998017770A1 (fr) * 1996-10-18 1998-04-30 Novo Nordisk Biochem North America, Inc. Procede de clarification de couleurs
US5789367A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789366A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789365A (en) * 1995-11-30 1998-08-04 Lever Brothers Division Of Conopco Inc. Detergent compositions containing soil release polymers
EP0586354B1 (fr) * 1992-07-31 1999-03-24 The Procter & Gamble Company Utilisation de polyesters modifiés pour enlever des graisses sur des tissus
US6255274B1 (en) 1999-02-16 2001-07-03 Clariant Gmbh Use of comb polymers as soil release polymers
US7285523B1 (en) * 1999-01-19 2007-10-23 Seydel Companies, Inc. Enzyme-containing granule and detergent composition
US8716211B2 (en) 2007-03-15 2014-05-06 Reckitt Benckiser N.V. Detergent composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012016462A1 (de) * 2012-08-18 2014-02-20 Clariant International Ltd. Verwendung von Polyestern in Wasch- und Reinigungsmitteln
JP7138554B2 (ja) * 2018-12-17 2022-09-16 ライオン株式会社 繊維製品用の液体洗浄剤組成物

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US4116885A (en) * 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
GB2095275A (en) * 1981-03-05 1982-09-29 Kao Corp Enzyme detergent composition
US4435307A (en) * 1980-04-30 1984-03-06 Novo Industri A/S Detergent cellulase
US4711730A (en) * 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4976879A (en) * 1987-10-05 1990-12-11 The Procter & Gamble Company Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
WO1991017243A1 (fr) * 1990-05-09 1991-11-14 Novo Nordisk A/S Preparation de cellulase comprenant un enzyme d'endoglucanase

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US4818569A (en) * 1987-10-05 1989-04-04 The Procter & Gamble Company Articles and methods for treating fabrics in clothes dryer
US4877896A (en) * 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US4908150A (en) * 1989-02-02 1990-03-13 Lever Brothers Company Stabilized lipolytic enzyme-containing liquid detergent composition
CA2027995C (fr) * 1989-10-31 1996-05-14 Stephen William Morrall Ester a groupe terminal sulfobenzoyle dans des oligomeres, utiles comme agent de lavage facilite dans des compositions de granules de detergents
SK19193A3 (en) * 1990-09-07 1993-07-07 Procter & Gamble Improved soil release agents for granular laudry detergents
ATE219136T1 (de) * 1991-01-16 2002-06-15 Procter & Gamble Kompakte waschmittelzusammensetzungen mit hochaktiven cellulasen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116885A (en) * 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
US4435307A (en) * 1980-04-30 1984-03-06 Novo Industri A/S Detergent cellulase
GB2095275A (en) * 1981-03-05 1982-09-29 Kao Corp Enzyme detergent composition
US4711730A (en) * 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4976879A (en) * 1987-10-05 1990-12-11 The Procter & Gamble Company Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
WO1991017243A1 (fr) * 1990-05-09 1991-11-14 Novo Nordisk A/S Preparation de cellulase comprenant un enzyme d'endoglucanase

Non-Patent Citations (1)

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Title
See also references of EP0641378A4 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0586354B1 (fr) * 1992-07-31 1999-03-24 The Procter & Gamble Company Utilisation de polyesters modifiés pour enlever des graisses sur des tissus
WO1996008554A1 (fr) * 1994-09-16 1996-03-21 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de blanchiment en poudre contenant des enzymes
WO1997019161A1 (fr) * 1995-11-20 1997-05-29 Henkel Kommanditgesellschaft Auf Aktien Preparation enzymatique contenant un polymere facilitant le lavage
US5789367A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789366A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789365A (en) * 1995-11-30 1998-08-04 Lever Brothers Division Of Conopco Inc. Detergent compositions containing soil release polymers
WO1998017770A1 (fr) * 1996-10-18 1998-04-30 Novo Nordisk Biochem North America, Inc. Procede de clarification de couleurs
US5919697A (en) * 1996-10-18 1999-07-06 Novo Nordisk A/S Color clarification methods
US7285523B1 (en) * 1999-01-19 2007-10-23 Seydel Companies, Inc. Enzyme-containing granule and detergent composition
US6255274B1 (en) 1999-02-16 2001-07-03 Clariant Gmbh Use of comb polymers as soil release polymers
US8716211B2 (en) 2007-03-15 2014-05-06 Reckitt Benckiser N.V. Detergent composition

Also Published As

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EG20531A (en) 1999-07-31
HU9402940D0 (en) 1995-03-28
HUT69329A (en) 1995-09-28
JPH07505670A (ja) 1995-06-22
EP0641378A1 (fr) 1995-03-08
EP0641378A4 (fr) 1995-08-09
CN1078747A (zh) 1993-11-24
MX9302143A (es) 1994-05-31
CA2117997A1 (fr) 1993-10-28
KR950700976A (ko) 1995-02-20
CZ248694A3 (en) 1995-05-17
BR9306245A (pt) 1998-06-23
MA22870A1 (fr) 1993-12-31
AU4279393A (en) 1993-11-18
IE930280A1 (en) 1993-10-20

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