WO1999058632A1 - Particule effervescente - Google Patents

Particule effervescente Download PDF

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Publication number
WO1999058632A1
WO1999058632A1 PCT/US1999/010007 US9910007W WO9958632A1 WO 1999058632 A1 WO1999058632 A1 WO 1999058632A1 US 9910007 W US9910007 W US 9910007W WO 9958632 A1 WO9958632 A1 WO 9958632A1
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WO
WIPO (PCT)
Prior art keywords
acid
alkyl
preferred
salt
anhydrous
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PCT/US1999/010007
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English (en)
Inventor
Gérard Marcel BAILLELY
Original Assignee
The Procter & Gamble Company
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Publication of WO1999058632A1 publication Critical patent/WO1999058632A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing compositions

Definitions

  • This invention relates to a effervescence particle and detergent compositions comprising the particle.
  • the inventors have found that a problem relating to these effervescence systems is that the presence of the acid lowers the pH of the washing water, which may not be desirable because certain detergent ingredients require an alkaline environment for maximum performance.
  • the inventors have now found that improved effervescence can be achieved when anhydrous perborate is used.
  • Anhydrous perborate has been mentioned as potential effervescence system, which upon contact with water provides oxygen gas.
  • US 4,4772,412 discloses a process for making a anhydrous perborate which can be used in liquid detergents. It mentions that the anhydrous perborate is unstable and losses performance when exposed to temperature increases or moisture. It states that a mixture of anhydrous perborate and high level of perborate monohydrate needs to be used to provide a more stable effervescence e component.
  • this material may only be suitable of compositions which allow the presence of bleaching species, i.e. perborate monohydrate. Furthermore, the inventors have found that this anhydrous perborate effervescence material is not suitable for use in most detergent products, in particular granular detergents.
  • the inventors have now found that the anhydrous perborate can be coated to improve its stability. They have found that the coated anhydrous perborate can easily be incorporated in detergent compositions, which are furthermore found to be stable upon storage. They have found that incorporation of coated perborate particles in detergent compositions provides excellent effervescence, even when small quantities are used, resulting in improved dispensing or dissolution of the detergent actives. Furthermore, the anhydrous perborate provides an alkaline environment, which ensures an better performance of certain detergent ingredients. Furthermore, they have found that no perborate monohydrate or no high levels of perborate monohydrate needs to be present in the particle of the invention, which makes the particle more weight and cost efficient and moreover which makes the particle suitable for nil-bleach compositions. Summary of the invention
  • the invention provides an effervescence particle comprising an anhydrous perborate salt which is coated with a coating material.
  • the invention also relates to processes for making this particle and detergent compositions comprising this particle.
  • the invention provides the use of a coated anhydrous perborate salt in a detergent composition for improvement of the dispensing and/ or dissolution of the composition into the washing water and/ or delivery of actives of the composition to the wash.
  • the coating agent of the particle in accord with the invention can be selected from any coating or disintegrant material known in the art, which is substantially non-hygroscopic, but which will disintegrate or partially dissolve upon contact with water, in particular under alkaline conditions in the wash, or is readily emulsified by surfactants present in the wash.
  • the coating agent may preferably be introduced on the anhydrous perborate salt in liquid or liquefied form, whilst preferably being solid or highly viscous at ambient temperature. Therefore, the coating agent preferably comprises one or more compounds which melt between 40°C to 80°C. Also preferred maybe that the coating agent is dusted unto the anhydrous perborate salt. It may be preferred that the coating agent has a secondary function in the washing process, for example as a builder or sequestering agent, softening agent or soil release agent.
  • the coating agent may comprise mixtures of any of the coating materials herein.
  • Preferred coating agents can be selected from the group comprising inorganic salts, preferably sodium or potassium sulphates or carbonates, waxes; paraffin oils; fatty acids and fatty alcohols; organic polymeric compounds, such as polycarboxyltes or acids thereof, polyethylene and/ or polypropylene glycols, polyamines, peptides; polyvinyl pyrrolidone and derivatives thereof; polyalkoxy, preferably polyethoxy fatty alcohols; nonionic surfactants, in particular nonionic alkoxylated surfactants, nonionic polyhydroxyfattyacid amide surfactants, nonionic fatty acid amide surfactants, nonionic alkylpolysaccharide surfactants, as described hereinafter; starches or sugars, including carboxymethyl starch, salts of starch glycolate, cellulose derivatives, including carboxy methyl celluloses and cross-linked modified celluloses; and inorganic minerals, preferably comprising clays, silicas, silicates and boros
  • coating agents for use herein comprise polymers or copolymers of maleic acid, acrylic acid and/ or methacrylic acid, or salts thereof; cellulose derivatives; nonionic surfactants; polyethylene and/or propylene glycols, particularly those of molecular weight 1000-20000, more particularly 2000 to 8000 and most preferably about 4000.
  • fatty acids examples include fatty acids, adipic acid and C8-C13 dicarboxylic acids, fatty alcohols, diols, esters and ethers.
  • Preferred fatty acids are those having a carbon chain length of from C12 to C22 and most preferably from C18 to C22.
  • Preferred dicarboxylic acids are adipic acid (C6), suberic acid (C8), azelaic acid (C9), sebacic acid (CIO), undecanedioic acid (Cl 1), dodecanedioic acid (C12) and tridecanedioic acid (C13).
  • Preferred fatty alcohols are those having a carbon chain length of from C12 to C22 and most preferably from C14 to C18.
  • Preferred diols are 1,2- octadecanediol and 1 ,2-hexadecanediol.
  • Preferred esters are tristearin, tripalmitin, methylbehenate, ethylstearate.
  • Preferred ethers are diethyleneglycol mono hexadecylether, diethyleneglycol mono octadecylether, diethyleneglycol mono tetradecylether, phenylether, ethyl naphtyl ether, 2 methoxynaphtalene, beta naphtyl methyl ether and glycerol monooctadecylether.
  • coating materials include dimethyl 2,2 propanol, 2 hexadecanol, 2 octadecanone, 2 hexadecanone, 2, 15 hexadecanedione and 2 hydroxybenzyl alcohol, C2-C13 dicarboxylic acids, fatty alcohols, diols, esters and ethers.
  • Preferred fatty acids are those having a carbon chain length of from C12 to C22 and most preferably from C18 to C22.
  • Preferred dicarboxylic acids are oxalic acid (C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid (C6), pimelic acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (CIO), undecanedioic acid (Cl 1), dodecanedioic acid (C12) and tridecanedioic acid (C13).
  • Preferred fatty alcohols are those having a carbon chain length of from C12 to C22 and most preferably from C14 to C18.
  • Preferred diols are 1 ,2-octadecanediol and 1,2-hexadecanediol.
  • Preferred esters are tristearin, tripalmitin, methylbehenate, ethylstearate.
  • Preferred ethers are diethyleneglycol mono hexadecylether, diethyleneglycol mono octadecylether, diethyleneglycol mono Otetradecylether, phenylether, ethyl naphtyl ether, 2 methoxynaphtalene, beta naphtyl methyl ether and glycerol monooctadecylether.
  • coating materials include dimethyl 2,2 propanol, 2 hexadecanol, 2 octadecanone, 2 hexadecanone, 2, 15 hexadecanedione and 2 hydroxybenzyl alcohol.
  • Highly preferred coating agents selected from the coating agents above comprise wax, paraffin oil, C 12 -C ⁇ 8 fatty acids, C 12 -C 18 polyhydroxy fatty acid amides, polyethylene glycols of average molecular weight of from 2000 to 20,000, preferably to 8000, polymeric polycarboxylates, modified starch and cellulose ether and derivatives thereof.
  • the coating agent can be introduced by any coating process known in the art.
  • the coating agent is applied in liquid or liquefied form.
  • Two preferred coating methods are a) coating with a molten coating agent and or b) coating with a nonaqueous solution of the agent.
  • the coating material is preferably applied at a temperature above its melting point, and solidifies on the tablet.
  • the coating is applied as a nonaqueous solution, the solvent being dried to leave a coherent coating.
  • the coating agent may preferably be applied to the anhydrous perborate salt by spraying, preferably by means of a controllable nozzle, or dipping.
  • a preferred process involves the use of a fluidised bed, as known in the art.
  • the process is performed at a temperature between 40°C and 200°C, or even 140°C or even 120°C, more preferably between 40°C and 80°C.
  • a coating of any desired thickness can be applied according to the present invention.
  • the particle comprises the coating agent at a level of from 0.3% to 20%, more preferably from 0.5% to 15% or even from 1% to 10% by weight of the particle.
  • the anhydrous perborate salt or oxoborate salt is preferably an anhydrous sodium or potassium perborate. It may be preferred that the direct product of the dehydration of a hydrated perborate salt, preferably sodium or potassium monohydrate, is incorporated in the particle of the invention. Then, depending on the conditions of the dehydration or drying process, e.g. the temperature, vacuum applied and air moisture content, certain amounts of hydrated perborate salt may be present in the product and in the particle of the invention.
  • hydrated perborate e.g. up to 20% or more preferably up to 15% or even up to 10% or even up to 5% by weight of the total amount of perborate salt.
  • the particle preferably has a particle size between 10 microns and 2 cm.
  • the particle is preferably such that 80% by weight of the particles has an particle size of more than 75 microns (more than 80% by weight of the particles on Tyler sieve mesh 200) and less thanl0% by weight of the particles has a particle size of more than 0.5 cm; preferably 80% by weight of the particles has an particle size of more than 100 microns (80% by weight on Tyler sieve mesh 100) and less than 10% by weight of the particles has a particle size of more than 0.1 cm; or more preferably 80% by weight of the particles has an particle size of more than 150 microns and less than 10% by weight of the particles has a particle size of more than to 5000 microns; it may be preferred that the particles have an average particle size of from 200 microns to 3000 microns, or even from 710 microns (on Tyler mesh sieve24) to 1180 microns (through Tyler mesh sieve 14).
  • the particle of the invention may comprise any diluent which does not react with anhydrous perborate salt and which is substantially anhydrous, meaning that no more than 2% by weight of free moisture is present, preferably no more than 1%, even more preferably no more than 0.5% by weight.
  • the free moisture content as used herein, can be determined by placing 5 grams of the substantially anhydrous component in a petri dish and placing this petri dish in a convection oven at 50°C for 2 hours, and subsequently measuring the weight loss, due to water evaporation.
  • the weight ratio of the anhydrous perborate salt to the diluent is preferably 10:1 to 1:10, more preferably from 5:1 to 1:5, more preferably from 3:1 to 1 :3.
  • Highly preferred diluents can comprises a polymeric organic compound or a anionic or nonionic surface active compound, preferably selected from the group comprising anionic alky sulphates or sulphonates, nonionic alkoxylated amides, alkyl esters of fatty acids, or alkoxylated alcohols, including polyethylene and/or propylene glycols, polymeric or oligomeric (poly) carboxilic acids or salts thereof, including polymeric or oligomeric acrylic/ maleic acids and salts thereof, alkoxylated fatty acid amides and alkoxylated alcoholamides, including ethanolamides and specific nonionic surfactants, including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants, alkyl esters of fatty acids and specific alkyl polysaccherides surfactant or mixtures of any of these nonionics compounds and anionic compounds, as described herein.
  • anionic alky sulphates or sulphonates preferably
  • the diluent comprises an organic or inorganic salt or acid.
  • the inorganic salts are silicate, sulphate, carbonate, borate (not being a perborate), phosphate, or halide, preferably chloride, preferably the sodium, potassium or optionally calcium or magnesium salts thereof.
  • the particle of the invention comprises a surface active component, which may be a diluent. It has been found that particles of the invention which comprise a surface active component and the effervescing anhydrous perborate salt provide improved foaming or sudsing in the wash. Any surface active component which is substantially anhydrous may be useful herein, as described hereinafter.
  • the particle of the invention is particularly useful in solid detergent or cleaning compositions, preferably in the form of granules, tablets, extrudates, bars or flakes.
  • the particle may be present as a separate particle or the it can be present as a part of a component of the detergent composition. It may be preferred that the compositions have a density of at least 400g/litre, more preferably at least 500g/litre.
  • compositions preferably contain one or more additional detergent components selected from surfactants, bleaches, builders, chelants, (additional) alkalinity sources, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, brighteners, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • additional detergent components selected from surfactants, bleaches, builders, chelants, (additional) alkalinity sources, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, brighteners, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Nonionic surfactants The compositions herein, and possibly the particle of the invention, preferably comprise one or more nonionic surfactants.
  • Preferred nonionic surfactants are selected from the group comprising alkyl sulfate surfactants and alkyl sulphonate surfactants, as described herein and in particular alkoxylated alcohols, including polyethylene and/or propylene glycols, alkoxylated fatty acid amides and alkoxylated alcoholamides, including ethanolamides and specific nonionic surfactants, including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants, alkyl esters of fatty acids and specific alkylpolysaccherides surfactant or mixtures of any of these nonionics compounds and anionic compounds, as described herein.
  • Highly preferred substantially anhydrous surface active components suitable in the compositions herein or in the aprticle of the invention are one or more nonionic surfactant, selected from the group of nonionic alkoxylated surfactants, including alkoxylated alcohol surfactants, polyhydroxyfattyacid amide surfactants, (alkoxylated) fatty acid amide surfactants and alkylpolysaccharide surfactants, or mixtures thereof, as described herein after.
  • nonionic surfactant selected from the group of nonionic alkoxylated surfactants, including alkoxylated alcohol surfactants, polyhydroxyfattyacid amide surfactants, (alkoxylated) fatty acid amide surfactants and alkylpolysaccharide surfactants, or mixtures thereof, as described herein after.
  • any alkoxylated nonionic surfactants can also be comprised in the compositions herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • nonionic alkoxylated alcohol surfactants being the condensation products of aliphatic alcohols with from 1 to 75, up to 50 moles, preferably 1 to 15 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are highly preferred nonionic surfactant comprised in the anhydrous component of the particles of the invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
  • Nonionic polyhydroxy fatty acid amide surfactant Nonionic polyhydroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides are highly preferred nonionic surfactant comprised in the compositions herein, in particular those having the structural formula R ⁇ CONR ⁇ Z wherein : Rl is H, Ci .jg, preferably C,-C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C] or C alkyl, most preferably Ci alkyl (i.e., methyl); and R 2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 or C 7 -C 19 alkyl or alkenyl, more preferably straight- chain C9-C17 alkyl or alkenyl, most preferably straight-chain C1 j-Cj 7 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the
  • a highly preferred nonionic polyhydroxy fatty acid amide surfactant for use herein is a C ⁇ -Ci4 > a C15-C17 and/or C ⁇ 6-Cjg alkyl N-methyl glucamide.
  • the polyhydroxy fatty acid amide can be prepared by any suitable process.
  • One particularly preferred process is described in detail in WO 9206984.
  • a product comprising about 95% by weight polyhydroxy fatty acid amide, low levels of undesired impurities such as fatty acid esters and cyclic amides, and which is molten typically above about 80°C, can be made by this process
  • Fatty acid amide surfactants or alkoxylated fatty acid amides can also be comprised compositions herein . They include those having the formula: R6C0N(R?) (R 8 ) wherein
  • R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 12 to 14 carbon atoms and R? an ⁇ R8 are each individually selected from the group consisting of hydrogen, C1 -C4 alkyl, Cj -C4 hydroxyalkyl, and -(C 2 H4 ⁇ ) x H, where x is in the range of from 1 to 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R 7 is different to R 8 > one having a smaller alkoxylation number than the other
  • Alkyl esters of fatty acids can also be comprised in the anhydrous material of the particle of the invention. They include those having the formula: R9COO(R10) wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R ⁇ is a C1 -C4 alkyl, C1 -C4 hydroxyalkyl, or -(C H4O) x H, where x is in the range of from 1 to 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that Rl is a methyl or ethyl group.
  • Alkylpolysaccharides can also be comprised in the surface active component of the foaming compoennt of the invention, such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • the composition herein preferably comprises one or more anionic surfactants.
  • Any anionic surfactant useful for detersive purposes is suitable. Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C- ⁇ -C « Stamm monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C fi -C 14 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • the anionic surfactant may preferably be present at a level of 1% to 90% by weight of the foaming component, preferably at a level of from 5% to 60%, and preferably of from 8% to 50% by weight of the component.
  • Anionic sulfate surfactant may preferably be present at a level of 1% to 90% by weight of the foaming component, preferably at a level of from 5% to 60%, and preferably of from 8% to 50% by weight of the component.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(C j -
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary Cc)-C 22 alkyl sulfates, more preferably the C1 ⁇ -C ⁇ $ branched chain alkyl sulfates and the C1 2 -Cj 4 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the ClO' lg alkyl sulfates which have been ethoxylated with from 0.5 to 50 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a *-T l"Cl , most preferably C1 1 -Cj 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C 2 Q linear or branched alkylbenzene sulfonates, alkyl ester sulfonates, in particular methyl ester sulphonates, Cg-C 22 primary or secondary alkane sulfonates, Cg-C 2 4 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH 2 CH 0) X
  • R is a C6 to Cj g alkyl group
  • x ranges from O to 10
  • the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR]-CHR -O) ⁇ -R3 wherein R is a Cg to Cjg alkyl group, x is from 1 to 25, Ri and R are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water- soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l- nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (Ri) CH 2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R 1 is a C1 -C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R 1 is a C1 -C4 alkyl group
  • M is an alkali metal ion.
  • a cationic surfactant may be comprised in the composition herein, preferably be present at a level of from 0.5% to 80% by weight of the component, more preferably from 1%> to 60%, most preferably from 3% to 50% by weight of the component.
  • the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixtures thereof.
  • the optional cationic mono-alkoxylated amine surfactant for use herein has the general formula:
  • R! is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 11 carbon atoms;
  • R ⁇ and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl;
  • R4 is selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is selected from C ⁇ -C4 alkoxy, especially ethoxy
  • R ⁇ is Cg-Cjg hydrocarbyl and mixtures thereof, preferably C6-C14, especially Cg-Ci 4 alkyl, preferably Cg , C ⁇ Q and C14 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH CH 2 O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH O] and
  • the cationic bis-alkoxylated amine surfactant for use herein has the general formula:
  • R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11, most preferably from about 8 to about 10 carbon atoms;
  • R ⁇ is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R ⁇ and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from Ci -C4 alkoxy, especially ethoxy, (i.e., -CH CH 2 O-), propoxy, butoxy and mixtures thereof;
  • p is from 1 to about
  • q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • R ⁇ is Cg-Ci g hydrocarbyl and mixtures thereof, preferably Cg, Cg, CI Q, CI , Cj4 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • R is C6-C1 g hydrocarbyl, preferably C5-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R ⁇ is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • Other compounds of the foregoing type include those wherein the ethoxy (CH 2 CH 2 O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH 2 O] and [CH 2 CH(CH3 ⁇ ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR4) X NO(R5) 2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C10-C1 g alkyl dimethylamine oxide, and Ci Q -lg acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be comprised in the surface active component of the composition of the invention or the compositions containing the particle of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R') 2 N + R2C00 ⁇ wherein R is a Cg-Ci g hydrocarbyl group, each R* is typically C1 -C3 alkyl, and R ⁇ is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ 2 _ ⁇ g dimethyl-ammonio hexanoate and the Ci 0-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • compositions herein comprise a suds suppressing system present at a level of from 0.01%) to 15%>, preferably from 0.05% to 10%, most preferably from O.P/o to 5%> by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C]g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound; wherein said silica/silicone antifoam compound is incorporated at a level of from 5%> to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 :1.1, at a level of from 0.5% to 10%), preferably 1% to 10%> by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a C ⁇ -C ⁇ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises an aluminosilicate, preferably Zeolite A, or a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • compositions herein preferably contain a water-soluble builder compound, typically present at a level of from 1%> to 80% by weight, preferably from 5% to 60% by weight, most preferably from 10%> to 40%> by weight of the composition or component.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • 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. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the component of the invention or the compositions containing the component of the invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 70% by weight, preferably from 5% to 60% by weight, most preferably from 10%> to 50% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) z (SiO 2 )y]. xH O wherein 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 material are in hydrated form and are preferably crystalline, containing from 4% to 30%, more preferably from 8% to 20% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [AlO 2 ) ⁇ 2 (SiO 2 ) 12 ]. xH 2 O
  • Zeolite X has the formula Nagg [(AlO 2 ) 86 (SiO 2 ) 10 6]. 276 H 2 O.
  • Preferred crystalline layered silicates for use herein have the general formula
  • x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is ⁇ -Na Si 2 05, available from Hoechst AG as
  • compositions of the invention or the cleaning composition may be a perhydrate bleach, such as hydrated metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na 2 CO3.3H O 2 , and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions or foaming components.
  • Organic peroxyacid bleaching system A preferred feature of the compositions herein, is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5%) to 6% by weight, more preferably from 1% to 40 by weight, most preferably from 1.5% to 25 by weight of the compositions or component
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to
  • R 3 i •s an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or
  • R , and Y is H or a solubilizing group. Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO, M , -CO 2 M , -SO, M , -N (R ).X and
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
  • TAED Tetraacetyl ethylene diamine
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • R ⁇ is an alkyl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10%) by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R ⁇ is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
  • compositions herein containing the particle of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 8%>, more preferably from 0.25% to 5 % and most preferably from 0.3%) to 4% by weight of the compositions or component
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1 , 1 diphosphonate or phosphonic acid.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, (di)ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • ethylenediaminotetracetic acid ethylenediaminotetracetic acid
  • EDDS ethylenediamine pentacetic acid
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3- sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-509,382 The ⁇ - alanine-N.N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide-N,N'-disuccinic acid Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.
  • Another preferred ingredient useful in the compositions containing the particle of the invention is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 20% of active enzyme by weight of the composition or component
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 12% by weight, preferably 0.001% to 10% by weight of the composition, and most preferably from 0.001% to 03% by weight of the composition.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 1, 1989.
  • Organic polymeric compounds are preferred additional components of the compositions containing the particle of the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 60%, preferably from 0.5%) to 25%, most preferably from 1% to 15%> by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • Another organic compound which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
  • X is a nonionic group selected from the group consisting of H, Ci -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • the cleaning compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • the cleaning compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, poly vinylpyrrolidonepolymers or combinations thereof.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N- O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R- group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water- solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • Polyvinylpyrrolidone The components or the compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the foaming component or cleaning compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxy ethyl
  • R is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R1 is anilino
  • R is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R1 is anilino
  • R 2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo ⁇ hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Cationic fabric softening agents can also be incorporated into the component of the invention or in compositions containing the component in accordance with the present invention.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5%) to 15% by weight, normally from 1% to 5%> by weight.
  • compositions herein of include highly preferably perfumes, bleach catalysts, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • the present foaming component or the cleaning compositions can have an acidic, neutral or an alkaline pH, depending on the application or the additional ingredients comprised in the component or composition.
  • the component or the compositions herein have a pH measured as a 1% solution in distilled water, of from 3 to 13.5, preferably least 4.0, preferably from to 12.5, most preferably from 5 to 12.0.
  • compositions can be made via a variety of methods, including dry-mixing, extruding, compressing and agglomerating of the various components comprised in the detergent composition.
  • the particle of the invention can be present in the cleaning compositions as a separate component of the composition, or can be part of or added to other components or compounds of the compositions.
  • the cleaning compositions can take a variety of physical forms including granular, extrudates tablet or bar forms.
  • the cleaning compositions are particularly the so-called concentrated granular detergent compositions or tablets adapted to be added to a washing machine by means of a dispensing drawer or by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the mean particle size of the base composition of granular cleaning compositions containing the foaming composition in accordance with the invention can be from 0.1 mm to 5.0 mm, but it should preferably be such that no more that 5% of particles are greater than 2.5mm in diameter, or even 1.7mm and that not more than 5% of particles are less than 0.15mm in diameter.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular cleaning or detergent compositions containing the particulate composition in accordance with the present invention typically have a bulk density of at least 300 g/litre, more preferably from 500 g/litre or even 650g/litre to 1200 g/litre, more preferably to 850 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities.
  • the cup It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry components of the invention or composition comprising the foaming component of the invention.
  • an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • TAS Sodium tallow alkyl sulfate
  • CxyEzS Sodium C ⁇ x -Cjy branched alkyl sulfate condensed with z moles of ethylene oxide MBAS ⁇ , y Sodium mid-chain branched alkyl sulfate having an average of x carbon atoms, whereof an average of y carbons comprised in (a) branching unit(s) C 48 SAS Sodium C 14 -C 18 secondary alcohol sulfate SADExS Sodium C ]4 -C 22 alkyl disulfate of formula 2-(R).C 4 H 7 -l,4-
  • Zeolite A II overdried Zeolite A I NaSKS-6 Crystalline layered silicate of formula ⁇ -Na 2 Si O5
  • Citric acid I Anhydrous citric acid Citric acid II Citric acid monohydrate Malic acid Anhydrous malic acid Carbonate I Anhydrous sodium carbonate with an average particle size between 200 ⁇ m and 900 ⁇ m Carbonate II Anhydrous sodium carbonate with an average particle size between lOO ⁇ m and 200 ⁇ m Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Silicate Amorphous Sodium Silicate SiO 2 :Na O; 2.0 ratio
  • NAC-OBS Nonanamido caproyl oxybenzene sulfonate in the form of the sodium salt.
  • NACA 6 nonylamino - 6 oxo - capronic acid NACA 6 nonylamino - 6 oxo - capronic acid.
  • SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to
  • the following tablet formulation comprises the particle of the invention:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une particule effervescente comprenant un sel de perborate anhydre enrobé d'un matériau d'enrobage. L'invention concerne également des procédés de fabrication de la particule, des compositions détergentes comprenant cette particule, ainsi que l'utilisation d'un sel de perborate anhydre enrobé dans une composition détergente pour améliorer la dispersion et/ou la dissolution de la composition détergente dans l'eau de lavage, et/ou pour favoriser la répartition des détergents actifs de la composition au cours du lavage.
PCT/US1999/010007 1998-05-08 1999-05-07 Particule effervescente WO1999058632A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9809693.6 1998-05-08
GB9809693A GB2337054A (en) 1998-05-08 1998-05-08 Effervescent particle

Publications (1)

Publication Number Publication Date
WO1999058632A1 true WO1999058632A1 (fr) 1999-11-18

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PCT/US1999/010007 WO1999058632A1 (fr) 1998-05-08 1999-05-07 Particule effervescente

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GB (1) GB2337054A (fr)
WO (1) WO1999058632A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440906B1 (en) 2000-11-03 2002-08-27 Chemlink Laboratories, Llc Solvent for liquid ingredients to be used in effervescent products
US6451746B1 (en) 2000-11-03 2002-09-17 Chemlink Laboratories, Llc Carrier for liquid ingredients to be used in effervescent products
US6491947B2 (en) 2000-11-03 2002-12-10 Chemlink Laboratories, Llc Expanded perborate salt, use, and method of production
US6866687B2 (en) 2002-09-27 2005-03-15 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Composition and method for bleaching a substrate
EP1633847A2 (fr) * 2003-05-30 2006-03-15 Orange Glo International, Inc. Preparations detergentes contenant des sels alcalins de peroxyde et des acides organiques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19957036A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Verfahren zur Herstellung teilchenförmiger Wasch- oder Reinigungsmittel
EP1754778A1 (fr) * 2005-08-19 2007-02-21 The Procter and Gamble Company Composition détèrgente solide pour lavage comprenant un sulphonate d'alkylbenzene comme un système détersive anionique et un système chelant
CN113372889B (zh) * 2021-06-23 2022-11-08 成都西油华巍科技有限公司 高失水堵漏剂

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3042621A (en) * 1957-11-01 1962-07-03 Colgate Palmolive Co Detergent composition
JPS5426988A (en) * 1977-08-03 1979-02-28 Nippon Peroxide Co Ltd Oxygen gas generating method
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
EP0358853A2 (fr) * 1988-06-18 1990-03-21 Henkel Kommanditgesellschaft auf Aktien Composés d'addition pour l'eau oxygénée stabilisants et sous forme de particules et leur utilisation
EP0360299A2 (fr) * 1984-03-16 1990-03-28 Warner-Lambert Company Composition effervescente pour le nettoyage des dentiers
US4965012A (en) * 1987-04-17 1990-10-23 Olson Keith E Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches
EP0634482A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions détergentes stabilisées

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3042621A (en) * 1957-11-01 1962-07-03 Colgate Palmolive Co Detergent composition
JPS5426988A (en) * 1977-08-03 1979-02-28 Nippon Peroxide Co Ltd Oxygen gas generating method
EP0360299A2 (fr) * 1984-03-16 1990-03-28 Warner-Lambert Company Composition effervescente pour le nettoyage des dentiers
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
US4965012A (en) * 1987-04-17 1990-10-23 Olson Keith E Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches
EP0358853A2 (fr) * 1988-06-18 1990-03-21 Henkel Kommanditgesellschaft auf Aktien Composés d'addition pour l'eau oxygénée stabilisants et sous forme de particules et leur utilisation
EP0634482A1 (fr) * 1993-07-14 1995-01-18 The Procter & Gamble Company Compositions détergentes stabilisées

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7914, Derwent World Patents Index; Class A82, AN 79-27044B, XP002111758 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6440906B1 (en) 2000-11-03 2002-08-27 Chemlink Laboratories, Llc Solvent for liquid ingredients to be used in effervescent products
US6451746B1 (en) 2000-11-03 2002-09-17 Chemlink Laboratories, Llc Carrier for liquid ingredients to be used in effervescent products
US6491947B2 (en) 2000-11-03 2002-12-10 Chemlink Laboratories, Llc Expanded perborate salt, use, and method of production
EP1345596A1 (fr) * 2000-11-03 2003-09-24 Chemlink Laboratories LLC Solvants pour ingredients liquides utilises dans des produits effervescents
EP1345596A4 (fr) * 2000-11-03 2004-03-24 Chemlink Lab Llc Solvants pour ingredients liquides utilises dans des produits effervescents
US6866687B2 (en) 2002-09-27 2005-03-15 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Composition and method for bleaching a substrate
EP1633847A2 (fr) * 2003-05-30 2006-03-15 Orange Glo International, Inc. Preparations detergentes contenant des sels alcalins de peroxyde et des acides organiques
EP1633847A4 (fr) * 2003-05-30 2007-04-11 Church & Dwight Co Inc Preparations detergentes contenant des sels alcalins de peroxyde et des acides organiques

Also Published As

Publication number Publication date
GB2337054A (en) 1999-11-10
GB9809693D0 (en) 1998-07-01

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