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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • 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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/364—Organic compounds containing phosphorus containing nitrogen
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/391—Oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3915—Sulfur-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• the invention relates to phosphate-free detergent bleach compositions.
• aluminosilicate built laundry detergent bleach compositions having improved cleaning and stain-removal performances, effective at low washing temperatures.
• phosphate detergency builders in laundry detergent compositions are well-known.
• phosphate builders such as the alkali metal triphosphates
• soluble phosphate species accelerate the eutrophication of water bodies.
• phosphate legislations have already forced detergent manufacturers to radically reduce the phosphate level of detergent compositions down to substantially zero. The need exists, therefore, for a built laundry detergent composition with zero phosphate level but which is comparable to a conventional triphosphate built composition in overall detergency effectiveness.
• zeolites Water-insoluble aluminosilicates, commonly known as zeolites, have been used in detergent compositions as important alternative builders to phosphates (see, for example, GB-A-­1429143; GB-A-1470250; GB-A-1504211; GB-A-1529454 and US-A-­4064062). Bleaching experiments have indicated, however, that the bleach performances of aluminosilicate built formulations are well below those of phosphate built products.
• EP-A-70079 it has been proposed to improve activated persalt bleach performance in aluminosilicate built compositions by addition thereto of a nitrilotriacetic acid compound (NTA). Apart from the still existing uncertainty around the use of NTA in various countries with regard to environmental consequences, the compositions as disclosed in EP-A-70079 are not particularly effective at temperatures around 40°C and below.
• NTA nitrilotriacetic acid compound
• the bleach system used therein comprises an inorganic peroxide compound and a peroxybenzoic acid bleach precursor as defined hereinafter combined with at least 0.5% by weight of a polyphosphonate sequestering agent.
• Polyphosphonates have already been suggested for use in detergent compositions containing aluminosilicates.
• German Offenlegungsschrift 2,544,035; 2,539,071; 2,527,388; 2,559,631 and Austrian Patent N o 338,947 all disclose the use of various polyphosphonates notably as dispersing agents in aluminosilicate built products.
• GB Patent 1,392,284 and GB Patent Application 2,113,730 discloses polyphosphonates, particularly ethylene diamine tetra methylene phosphonic acid, as peroxide bleach stabilizer.
• aluminosilicate built detergent compositions which contain 0.01-4% by weight of a polyphosphonate sequestering agent and 5-25% by weight of citric acid, citrates or a bicarbonate as pH-regulating agent. These compositions still contain a phosphate builder and are furthermore unsatisfactory when used for washing at the low wash temperature region of 40°C and below.
• the detergent composition of the invention necessarily contains a peroxybenzoic acid bleach precursor as the bleach activator, which on perhydrolysis generates a peroxybenzoic acid.
• a peroxybenzoic acid bleach precursor as the bleach activator, which on perhydrolysis generates a peroxybenzoic acid.
• Other bleach precursors such as the most commonly used tetraacetylene diamine (TAED), which generates peracetic acid, are much less effective and hence unsuitable for use in the present invention.
• TAED tetraacetylene diamine
• Peroxybenzoic acid precursors are known in the art, e.g. from GB-A-836988. Examples thereof are phenylbenzoate; phenyl p-­nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenyl benzoate; sodium or potassium benzoyloxy benzenesulphonate; and benzoic anhydride.
• the peroxybenzoic acid precursor compounds usable in the present invention have the formula: wherein X is H, NO2, C1-C4 straight or branched chain alkyl, Cl or Br; and Y is H, CO2 ⁇ M+, SO3 ⁇ M+, SO4 ⁇ M+, NO2, Cl or Br; M being a water-soluble cation, preferably alkali metal cation, particularly Na+ or K+.
• the invention provides a phosphate-free detergent bleach composition
• a phosphate-free detergent bleach composition comprising at least one detergent-active material in an amount of 5% to 40% by weight, a water-insoluble aluminosilicate cation exchange material as main builder in an amount of from 15% to about 40% by weight, and from 0.5% to about 3% by weight of a polyphosphonate compound of the formula: wherein each R1 is CH2PO3H2 or a water-soluble salt thereof, and m is an integer having the value of 0, 1 or 2, characterized in that the composition further contains from about 5% to about 35% by weight of an inorganic peroxide compound, and from about 1% to about 10% by weight of a peroxy benzoic acid bleach precursor having the formula: wherein X is H, NO2, C1-C4 straight or branched chain alkyl, Cl or Br; and Y is H, CO2 ⁇ M+, SO3 ⁇ M+, SO4 ⁇ M+, NO2, Cl or Br; M being a water-soluble
• a preferred peroxybenzoic acid bleach precursor is sodium p-­benzoyloxy benzenesulphonate of the formula :
• Another preferred peroxybenzoic acid bleach precursor is p-­tert-butyl benzoyloxy benzenesulphonate.
• the inorganic peroxide compounds usable in the present invention can be true persalts or perhydrates, which liberate hydrogen peroxide in aqueous solution.
• examples of inorganic peroxide compounds are the alkali metal perborates, percarbonates, perphosphates and persilicates, the perborates, particularly sodium perborate tetra- and monohydrate being preferred because of their commercial availability.
• the inorganic peroxide compound and the peroxybenzoic acid bleach precursor in the composition of the invention may be present in a molar ratio of between 0.5:1 and about 20:1, preferably from 1:1 to 10:1. Under certain wash conditions such as are commonly used in the U.S.A. a molar ratio of about 2:1 may be of advantage.
• composition of the invention contains at least one detergent-active material which can be an organic soap or synthetic detergent surfactant material.
• an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, soap, or mixtures thereof is included.
• Many suitable detergent-active compounds are commercially available and are fully described in literature, for example in US-A-4222905 and US-A-4239659 and in "Surface Active Agents and Detergents", Vol. I and II, by Schwartz, Perry and Berch.
• the preferred detergent-active compounds which can be used are synthetic anionic, soap and nonionic compounds.
• the first-mentioned are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
• suitable synthetic, anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especia­lly those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of
• Suitable soaps are the alkali metal salts of long chain C8-C22 fatty acids such as the sodium soaps of tallow, coconut oil, palmkernel oil, palm oil or hardened rapeseed oil fatty acids or mixtures thereof.
• the preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium (C16-C18) alkyl sulphates.
• nonionic detergent compounds examples include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
• alkylene oxides usually ethylene oxide
• alkyl (C6-C22) phenols generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule
• condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide generally 6 to 30 EO
• nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
• detergent-active compounds for example mixed anionic or mixed anionic and nonionic compounds
• Amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the compositions of the invention, but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic, detergent-active compounds are used, it is generally in small amounts in the compositions based on the much more commonly used synthetic anionic and/or nonionic detergent-active compounds.
• the detergent composition of the invention also contains a water-insoluble aluminosilicate cation-exchange material in an amount of from 15% to about 40% by weight, preferably from 20% to 35% by weight.
• the aluminosilicate can be crystalline or amorphous in character, preferred materials having the unit cell formula I: M z [(AlO2) z (SiO2) y ] xH2O I wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is from about 1.0 to about 0.5 and x is at least 5, preferably from about 7.5 to about 276, more preferably from about 10 to about 264.
• the alumino­silicate materials are in hydrated form and are preferably crystalline containing from about 10% to about 28%, more preferably from about 18% to about 22% water.
• the aluminosilicate ion-exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns, preferably from about 0.2 micron to about 4 microns.
• 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 herein are usually further characteri­zed by their calcium ion-exchange capacity, which is at least about 200 mg.
• aluminosilicate ion- exchange materials herein are still further characterized by their calcium ion-­exchange rate which is at least about 2 grains Ca++/gallon/­minute/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/ gallon/minute/gram/gallon to about 6 grains/gallon/minute/­gram/gallon, based on calcium ion hardness.
• Optimum aluminosilicates for builder purposes exhibit a calcium ion-­exchange rate of at least about 4 grains/gallon/minute/gram/­gallon.
• Aluminosilicate ion-exchange materials useful in the practice of this invention are commercially available and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion-exchange materials is discussed in US-A-3985669.
• Preferred synthetic crystalline aluminosilicate ion-exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
• the crystalline aluminosilicate ion-exchange material is Zeolite A and has the formula: Na12[AlO2)12 (SiO2)12] xH2O wherein x is from about 20 to about 30, especially about 27.
• Zeolite X of formula Na86 [(AlO2)86)(SiO2)106] .276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(AlO2)6 (SiO2)6] 7.5 H2O).
• polyphosphonate compounds usable in the present invention are as defined hereinbefore. Effectively, the amount of polyphosphonate compound in the composition is from 0.5% to about 3% by weight. Amounts of lower than 0.5% are inadequate to give the desired benefit, and levels of higher than 3% by weight will give no added benefit. A preferred level of polyphosphonate compound is from 1% to 2% by weight of the composition.
• Suitable polyphosphonate compounds are, for example, aminotri­(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid) and diethylene triamine penta(methylene phosphonic acid).
• a preferred polyphosphonate compound is ethylene diamine tetra(methylene phosphonic acid) or its water-soluble salts, known as EDTMP, which is preferably used in the form of its calcium complex, i.e. Ca n -EDTMP (n being from 1-3), as disclosed in US-A-4,259,200.
• the composition of the invention will also include an enzyme, particularly proteolytic enzymes.
• Suitable proteolytic enzymes are normally solid, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
• proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the composition of the present invention.
• suitable proteolytic enxymes are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis , such as the commercially available subtilisins Maxatase®, as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase®, as supplied by Novo Industri A/S, Copenhagen, Denmark.
• protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade names Esperase® and Savinase® .
• the preparation of these and analogous enzymes is described in British Patent Specification N o 1,243,784.
• the amount of proteolytic enzymes used in the composition of the invention ranges from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, depending upon their activity. They are generally incorporated in the form of granules, prills or "marumes" in an amount such that the final washing product has a proteolytic activity of from about 2-20 Anson units per kilogram of final product.
• the detergent composition herein can contain any of the conventional additives and adjuncts in the amounts in which such materials are normally employed in fabric washing compositions.
• additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel and coconut fatty acids; lather depressants such as alkyl phosphates, silicones and waxes; anti-­redeposition agents such as sodium carboxymethyl cellulose (SCMC), polyvinyl pyrrolidone (PVP) and the cellulose ethers such as methylcellulose and ethyl hydroxyethyl cellulose; stabilizers such as ethylene diamine tetraacetate; fabric-­softening agents; inorganic salts such as sodium sulphate and sodium carbonate; and - usually present in very minor amounts - fluorescent agents, perfumes, other enzymes such as proteases, amylases and lipases; germicides and colourants.
• lather boosters such as alkanolamides, particularly the
• Polycarboxylate polymers though not essential, may also be included as desired in amounts of from e.g. about 0.5% to 6% by weight of the total composition.
• the polycarboxylate polymers herein are preferably selected from co-polymeric polycarboxylic acids and their salts derived from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid or mesaconic acid as a first monomer and ethylene, methyl vinyl ether, acrylic acid or metacrylic acid as a second monomer, the co-polymer comprising at least about 10 mole%, preferably at least about 20 mole% of polycarboxylic acid units and having weight average molecular weights of at least about 10,000, preferably at least about 30,000; homopolyacrylates and homopolymethacrylates having a weight average molecular weight of from about 1000 to about 100,000, preferably from about 5000 to about 50,000; and mixtures thereof.
• the detergent compositions of the invention are preferably presented in free-flowing particulate, e.g. powdered or granular form, and can be produced by any of the known techniques commonly employed in the manufacture of such washing compositions, but preferably by spray-drying an aqueous slurry comprising the surfactant(s) and the alumino­silicate to form a detergent base powder, to which the heat-­sensitive ingredients are added, including the perbenzoic acid bleach precursor, the inorganic percompound, enzymes and optionally some other ingredients as conveniently desirable.
• the polyphosphonate compound may be present in the base powder, but is preferably added as calcium phosphonate to the spray-dried base powder.
• the bleach precursor and enzymes are preferably added as granulated particles. It is preferred that the process used to form the compositions should result in a product having a moisture content of up to about 15%, more preferably from about 7% to about 14% by weight.
• composition A Parts by weight Sodium linear alkylbenzene sulphonate 9.0 Fatty alcohol-7 ethoxylate 1.5
• Maleic acid/acrylic acid copolymer Sokalan ® CP5 ex BASF
• 4.0 Sodium aluminosilicate Zeolite A 24.0
• Sodium sulphate anhydrous
• EDTA ethylenediamine tetraacetate
• Na2CO3 Sodium carbonate
• Composition B Sodium perborate monohydrate 13.0 Anti-foaming agent 2.5
• Proteolytic enzyme Savinase ex NOVO
• composition A or composition B can be separately packed in two unit sachets or in a two-compartment unit sachet or presented as a combined fully formulated powder composition.

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• 1987
  • 1987-12-04 GB GB878728386A patent/GB8728386D0/en active Pending
• 1988
  • 1988-10-21 EP EP88202355A patent/EP0319054A3/fr not_active Withdrawn
  • 1988-10-26 NO NO88884760A patent/NO884760L/no unknown
  • 1988-11-02 AU AU24597/88A patent/AU604985B2/en not_active Ceased
  • 1988-11-08 BR BR888805817A patent/BR8805817A/pt unknown
  • 1988-11-25 KR KR1019880015542A patent/KR920004719B1/ko active IP Right Grant
  • 1988-12-02 JP JP63305866A patent/JPH01188596A/ja active Pending

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