WO1994003395A1 - Compositions de precurseurs de blanchiment a base de peroxyacide - Google Patents

Compositions de precurseurs de blanchiment a base de peroxyacide Download PDF

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Publication number
WO1994003395A1
WO1994003395A1 PCT/US1993/006801 US9306801W WO9403395A1 WO 1994003395 A1 WO1994003395 A1 WO 1994003395A1 US 9306801 W US9306801 W US 9306801W WO 9403395 A1 WO9403395 A1 WO 9403395A1
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Prior art keywords
composition
composition according
weight
precursor
polymers
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PCT/US1993/006801
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English (en)
Inventor
Anthony Dovey
Douglas Gilbert Fraser
Graham Alexander Sorrie
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU47770/93A priority Critical patent/AU4777093A/en
Priority to JP6505341A priority patent/JPH09502208A/ja
Priority to EP93918259A priority patent/EP0652848A4/fr
Publication of WO1994003395A1 publication Critical patent/WO1994003395A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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

Definitions

  • This invention relates to solid peroxy acid bleach precursor compositions and especially to particulate detergent compositions incorporating inorganic perhydrate bleaches together with N- or O- acyl group - containing peroxycarboxylic acid bleach precursors (so-called bleach activators) .
  • Bleach precursor compositions have come into widespread use in recent years as heavy duty fabric cleaning products, particularly in automatic washing machines.
  • the growth in usage of bleach activators has mirrored a decrease in fabric wash temperatures which itself has accompanied an increase in the proportion of fabrics that are coloured.
  • the prior art contains numerous examples of bleach activators coated or agglomerated so as to increase their stability on storage in detergent compositions and/or to influence their solution behaviour.
  • EP-A-0070474 discloses granulate bleach activators prepared by spray drying an aqueous pumpable dispersion containing an N-acyl or O-acyl compound together with at least one water-soluble cellulose ether, starch or starch derivative in a weight ratio of activator to coating of from 98:2 to 90:10.
  • GB-A-1507312 discloses the coating of bleach activators with a mixture of alkali metal C 8 - C 2 fatty acid salts in admixture with the corresponding fatty acids.
  • GB-A- 1381121 employs a molten coating of inter alia C ⁇ ⁇ - C 18 fatty acid mixtures to protect solid bleach activators.
  • GB-A-1441416 discloses a similar process employing a mixture of C 1 ⁇ c 14 fatty acids and C 10 ⁇ 20 aliphatic alcohols.
  • EP-A-0375241 describes stabilised bleach activator extrudates in which C5-C 13 alkyl peroxy carboxylic acid precursors are mixed with a binder selected from anionic and nonionic surfactants, film forming polymers fatty acids or mixtures of such binders.
  • EP-A-0356700 discloses compositions comprising a bleach activator, a water-soluble film forming polymer and 2-15% of a C 3 -C 6 polyvalent carboxylic acid or hydroxycarboxylic acid for enhanced stability and ease of dispersion/solubility.
  • the carboxylic acid of which a preferred example is citric acid, is dry mixed with the bleach activator and then granulated with the film forming polymer. The citric acid is asserted to provide an enhanced rate of dissolution of the bleach activator granules.
  • EP-A-0382464 concerns a process for coating or encapsulation of solid particles including bleaching compounds and bleach activators in which a melt is formed of coating material in which the particles form a disperse phase, the melt is destabilised and then caused to crumble to a particulate material in which the disperse phase particles are embedded in the continuous (coating) phase.
  • coating materials are disclosed and certain materials such as polyacrylic acid and cellulose acetate phthalate are taught as being useful where release of the coated material is dependent on pH.
  • compositions of the prior art relate to the storage and handling properties of said compositions, and is thus an additional object of the present invention to provide a bleach precursor composition as a free-flowable powder which remains as such throughout prolonged storage time.
  • Co-pending application GB-91-02507.2 proposes to use various water-soluble organic materials, including certain monomeric and olygomeric carboxylates as coating materials for such bleach precursor compositions.
  • the present invention is directed to a solid peroxyacid bleach precursor composition
  • a solid peroxyacid bleach precursor composition comprising a particulate peroxyacid bleach precursor material, said precursor comprising one or more N-, or O- acyl groups and having a Mpt>30°C, wherein said precursor is coated with a coating material, characterized in that said coating material is selected from water-soluble acidic polymers, wherein said polymers have a water solubility greater than 5 g/1 at 20°C, a molecular weight of from 1000 to 250,000, preferably 1500 to 150,000, and wherein a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
  • said precursor is co-agglomerated with a said water-soluble acidic polymer before it is coated.
  • the solid peroxyacid bleach precursor compositions of the present invention incorporate precursors containing 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 and acylated derivatives of imidazoles and oxi es, and examples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred classes are esters such as are disclosed in GB-A-836988, 864,798, 1147871 and 2143231 and imides such as are disclosed in GB-A-855735 & 1246338. Particularly preferred precursor compounds are the N- ,N,N 1 N 1 tetra acetylated compounds of formula
  • x can be 0 or an integer between 1 & 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD tetraacetyl hexylene diamine
  • Solid peroxyacid bleach precursors useful in the present invention have a Mpt>30°C and preferably >40°C. Such precursors will normally be in fine powder or crystalline form in which at least 90% by weight of the powder has a particle size ⁇ 150 micrometers.
  • compositions according to the present invention Another essential ingredient of the compositions according to the present invention is a water-soluble acidic polymer.
  • Said polymer is used in the compositions according to the present invention as the coating material to coat said peroxyacid bleach precursor.
  • said peroxyacid bleach precursor is co-agglomerated before it is coated, preferably with a said water-soluble acidic polymer.
  • the binder material and the coating material are different water-soluble acidic polymers, but in another, preferred embodiment of the present invention, the binder material and the coating material are the same water-soluble acidic polymer.
  • Suitable polymers for use herein are water-soluble. By water-soluble, it is meant herein that the polymers have a solubility greater than 5 g/1 at 20°C.
  • Suitable polymers for use herein are acidic.
  • acidic it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
  • Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000, preferably, suitable polymers for use herein have a melting point superior to 30°C.
  • Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention, include those having the following empirical formula I :
  • the proportion of M being H in such polymers must be such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
  • Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-1, 597 , 756.
  • Preferred polycarboxylate polymers fall into several categories.
  • a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha - ⁇ .4 alkyl acrylic acid as second monomer.
  • preferred polycarboxylate polymers of this type are those in which X is CH 2 , R 3 is H or CT ⁇ alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
  • Such polymers are available from BASF under the trade name Sokalan( R ) CP5 (neutralized form) and Sokalan( R ) CP45 (acidic form) .
  • a second category belongs to the class of polycarboxylate polymers in which, referring to formula I, X is CH 2 , R 3 is
  • OH, p is from 0 to 0.1, preferably 0 and n averages from about 50 to about 1500, preferably from about 100 to 1000.
  • Y if present, can be a polycarboxylic acid such as II above, or an ethylene oxide moiety.
  • a third category belongs to the class of acetal polycarboxylate polymers in which, referring to formula I, X is (0R 4 ) 2 where R4 is C1-C4 alkyl , R 3 is H, p is from 0 to 0.1, preferably 0 and n averages from 10 to 500. If present, Y again can be a polycarboxylic acid such as II above or an ethyleneoxide moiety.
  • a fourth category belongs to the class of polycarboxylate polymers in which referring to formula I, X is CH , R 3 is H or C ⁇ ⁇ .4 alkyl, p is 0 and n averages from about 10 to
  • 1500 preferably from about 500 to 1000.
  • a fifth category of polycarboxylate polymers has the formula I in which X is CH 2 , R 3 is H or Cl-4 alkyl, especially methyl, p is from 0.01 to 0.09, preferably from 0.02 to 0.06, n averages from about 10 to about 1500, preferably from about 15 to about 300 and Y is a polycarboxylic acid formed from maleic acid, citraconic acid,m itaconic acid or mesaconic acid, highly preferred being maleic acid-derived comonomers of formula II above.
  • the bleach-stable polymer end groups in formula I suitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof.
  • M is H or mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium.
  • the proportion of M which is H is such as to ensure that -the polymer meets the pH criteria described herein above.
  • n the degree of polymerization of the polymer can be determined from the weight average polymer molecular weight by dividing the latter by the average monomer molecular weight.
  • n 182 (i.e. 15,500/(116 x 0.3 + 72 x 0.7) .
  • weight-average polymer molecular weights can be determined herein by gel permeation chromotography using Water [mu] Porasil (RTM) GPC 60 A2 and [mu] Bondagel (RTM) E-125, E-500 and E-1000 in series, temperature- controlled columns at 40°C against sodium polystyrene sulphonate polymer standards, available from Polymer Laboratories Ltd. , Shropshire, UK, the polymer standards being 0.15M sodium dihydrogen phosphate and 0.02M tetramethyl ammonium hydroxide at pH 7.0 in 80/20 water/acetonitrile.
  • Mixtures of polycarboxylate polymers are also suitable herein, especially mixtures comprising a high molecular weight component having an n value of at least 100, preferably at least 120, and a low molecular weight component having an n value of less than 100, preferably from 10 to 90, more preferably from 20 to 80.
  • Such mixtures are optimum from the viewpoint of providing excellent bleach stability and anti-incrustation performance in the context of a zerophosphate detergent formula.
  • the weight ratio of high molecular weight component to low molecular weight component is generally at least 1:1, preferably from about 1:1 to about 20:1, more preferably from about 1.5:1 to about 10.1, especially from about 2:1 to about 8:1.
  • Preferred polycarboxylate polymers of the low molecular weight type are polycarboxylate polymers of the fourth category (ho opolyacrylate polymers) listed above.
  • highly preferred polycarboxylate polymers herein are those of the first category in which n averages from 100 to 800, preferalby from 120 to 400 and mixtures thereof with polycarboxylate polymers of the fourth category in which n averages from 10 to 90, preferably from 20 to 80.
  • polymers for use herein include polymers derived from amino acids such as polyglutamine acid, as disclosed in co-pending application GB 91-20653.2, and polyaspartic acid, as disclosed in EP 305 282, and EP 351 629.
  • a process for manufacturing a preferred solid peroxyacid bleach precursor according to the present invention includes the steps of :
  • the peroxyacid bleach precursor powder must be co-agglomerated into a water-soluble acidic polymer binder material as hereinabefore defined. Any agglomerating technique known to the man skilled in the art is suitable for use herein.
  • the co-agglomerated particulate material does not itself provide the full benefits of the invention, and said co- agglomerated material needs to be coated with a water- soluble acidic polymer as hereinabove defined.
  • the coating of the co-agglomerated material with the coating material can be carried out in several ways:
  • the coating material may be sprayed on as a molten material or as a solution or dispersion in a solvent/carrier liquid which is subsequently removed by evaporation.
  • the coating material can also be applied as a powder coating e.g. by electrostatic techniques although this is less preferred as the adherence of powdered coating material is more difficult to achieve and can be more expensive.
  • Molten coating is a preferred technique for coating materials of Mpt ⁇ 80°C but is less convenient for higher Melting Point acids (i.e. >100°C) .
  • spray on as a solution or dispersion is preferred.
  • Organic solvents such as ethyl and isopropyl alcohol can be used to form the solutions or dispersions, although this will necessitate a solvent recovery stage in order to make their use economic.
  • organic solvents also gives rise to safety problems such as flammability and operator safety and thus aqueous solutions or dispersions are preferred.
  • Aqueous solutions are particularly advantageous as the coating materials herein have a high aqueous solubility, provided the solution has a sufficiently low viscosity to enable it to be handled.
  • a concentration of at least 25% by weight of the coating material in the solvent is used in order to reduce the drying/evaporation load after surface treatment has taken place.
  • the treatment apparatus can be any of those normally used for this purpose, such as inclined rotary pans, rotary drums and fluidised beds.
  • the solid peroxyacid bleach precursor compositions according to the present invention comprise from 30% to 93% by weight of the total composition of said peroxyacid bleach precursor, preferably 70% to 88% and from 7% to 60% of said polymer, preferably 12 % to 30%.
  • the solid peroxyacid bleach precursor compositions according to the present invention comprise particles of different sizes which can be separated using sieves. Another advantage of the present invention is that it allows to use peroxyacid bleach precursor particles of smaller size than the compositions of the prior art, thus allowing significant improvement in the bleaching performance without increasing fabric damage. Accordingly, in a preferred embodiment of the present invention, said particles have a particle size ranging from 100 micrometers to 1700 micrometers, i.e. said particles pass through a sieve of 1700 micrometers and do not pass through a sieve of 100 micrometers, with a mean particle size of from 250 to 800 micrometers. As used herein, the mean particle size refers to the weighted average particle size in the total composition. In a further preferred embodiment, particles in the composition range from 150 to 1700 micrometers, most preferably 250 to 1700 micrometers, with a preferred mean particle size of from 400 to 600 micrometers, most preferably 450 to 550 micrometers.
  • the compositions according to the present invention have a mean coating level of from 2% to 25% by weight of the total composition, preferably 5% to 15%, and the coating level for any given particle, or the mean coating level for any particle class, ranges from -15% to +15% of the mean coating level of the composition.
  • the mean coating level refers to the weight % of coating material in the total composition.
  • the mean coating level of a particle class refers to the weight % of coating material in the particles of a given size class.
  • the amount of coating material in a given sample can be determined by a variety of methods, including colorimetric titration with ferrothiocyanate, photometric titration with chro otropes, gas chromatography etc.
  • a preferred and simple method is an acid-base titration calibrated with the polymer.
  • the amount of coating material can be calculated by determining the amount of polymer in an agglomerated but uncoated sample, then measuring the amount of polymer in an agglomerated and coated sample of same weight, then calculating the difference between both samples.
  • Solid peroxyacid bleach precursor compositions in accordance with the invention can be used in a variety of applications.
  • the peroxyacid bleach compositions may themselves be incorporated into other solid compositions such as tablets, extrudates and agglomerates.
  • the compositions can also be suspended in nonaqueous liquid compositions in which the organic acid surface treating material is insoluble and inert.
  • the preferred application for the solid peroxybleach precursor compositions of the invention is as particulate components of granular detergent compositions, particularly the so- called concentrated detergent compositions that are added to a washing machine by means of a dosing device placed in the machine drum with the soiled fabric load.
  • Concentrated granular detergent compositions dispensed into the wash liquor via a dosing device are more subject to dissolution problems than compositions added via the dispensing compartment of a washing machine because, in the initial stages of a wash cycle, the agitation in the immediate environment of the product is inhibited by the presence of the fabric load. Whilst this can constitute a benefit in permitting the development of high transient concentrations of builder and surfactant, the development of high transient peroxyacid concentrations can, as noted previously, lead to fabric and colour damage.
  • the compositions of the present invention when incorporated into concentrated detergent products delivered to the wash liquor via a dispensing device, mitigate if not eliminate this problem.
  • Detergent compositions incorporating the coated peroxy acid bleach precursor particulates will normally contain from 0.5% to 20% of the precursor, more frequently from 1% lo to 9% and most preferably from 3% to 8%, on a composition weight basis.
  • Such detergent compositions will, of course, contain a source of alkaline hydrogen peroxide necessary to form a peroxyacid bleaching species in the wash solution and preferably will also contain other components conventional in detergent compositions.
  • preferred detergent compositions will incorporate one of more of surfactants, organic and inorganic builders, soil suspending and anti- redeposition agents, suds suppressors, enzymes, fluorescent whitening agents, photo activated bleaches, perfumes and colours.
  • Detergent compositions incorporating the coated particulate peroxyacid precursors of the present invention will include an inorganic perhydrate bleach, normally in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor.
  • This perhydrate is normally incorporated at a level of from 3% to 35% by weight, more preferably from 5% to 30% by weight and most preferably from 8% to 25% by weight of the composition.
  • the perhydrate may be any of the inorganic salts such as perborate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate. Whilst fabric colour damage arising from compositions in accordance with the invention is low, irrespective of whether a perborate or percarbonate salt is employed, the improvement in comparison with uncoated precursor particulates is more noticeable with percarbonate bleach as this causes greater fabric colour damage in the absence of any coating on the bleach precursor.
  • Sodium percarbonate which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na 2 C0 3 .3H 2 0 2 , and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
  • EDTA 1-hydroxyethylidene 1, 1-diphosphonic acid
  • HEDP 1-diphosphonic acid
  • the percarbonate can be incorporated into detergent compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material.
  • a suitable coating is sodium silicate of Si0 2 :Na 2 0 ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate.
  • Another coating is a mixed salt of an alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:200 to
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na 2 S0 4 .n.Na 2 C0 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Magnesium silicate can also be included in the coating.
  • the particle size range of the crystalline percarbonate is from 350 micrometers to 450 micrometers with a mean of approximately 400 micrometers.
  • 60% to 80% by weight of the crystals have a size greater than 425 micrometers, with a mean of approximately 650 micrometers.
  • the percarbonate Whilst heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, the percarbonate still requires protection from heavy metals present as impurities in other ingredients of the product. Accordingly, in detergent compositions utilising percarbonate as the perhydrate salt, the total level of Iron, Copper and Manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability. Detergent compositions in which alkali metal percarbonate bleach has enhanced stability are disclosed in the Applicants copending British Patent Application No. 9021761.3 (Attorney's Docket No. CM343) .
  • a wide range of surfactants can be used in the detergent compositions.
  • a list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
  • Mixtures of anionic surfactants are suitable herein, particularly blends of sulphate, sulphonate and/or carboxylate surfactants.
  • Mixtures of sulphonate and sulphate surfactants are normally employed in a sulphonate to sulphate weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 12 -C ⁇ s fatty source, preferably from a C ⁇ g-C 18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants in such sulphonate sulphate mixtures are alkyl sulphates having from 12 to 22, preferably 16 to 18 carbon atoms in the alkyl radical.
  • Another useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other.
  • One such system comprises a mixture of C 1 -C 15 alkyl sulphate and C 16 -C 18 alkyl sulphate in a weight ratio of ⁇ 4 -0 ⁇ 5 : Ci 6 ⁇ c 18 of from 3:1 to 1:1.
  • alkyl sulphates may also be combined with alkyl ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • the cation in each instance is again an alkali metal, preferably sodium.
  • anionic surfactants suitable for the purposes of the invention are the alkali metal sarcosinates of formula
  • R-CON (R) CH 2 COOM wherin R is a C 9 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C1-C 4 alkyl group and M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C 12 - c 14 . / myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • One class of nonionic surfactants useful in the present invention comprises condensates of ethylene oxide with a hydrophobic moiety, providing surfactants having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants of this type are the Cg-C ⁇ primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 1 -C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C 12 -C 1 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3 ; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C 8 -C 2 Q, preferably C]_o ⁇ c 14 N-alkyl or alkenyl amine oxides and propylene-1, 3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C jj -C ⁇ , preferably C ⁇ Q -
  • N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the detergent compositions comprise from 5% to 20% of surfactant but more usually comprise from 7% to 20%, more preferably from 10% to 15% surfactant by weight of the compositions.
  • Combinations of surfactant types are preferred, more especially anionic-nonionic and also anionic-nonionic- cationic blends. Particularly preferred combinations are described in GB-A-2040987 and EP-A-0087914. Although the surfactants can be incorporated into the compositions as mixtures, it is preferable to control the point of addition of each surfactant in order to optimise the physical characteristics of the composition and avoid processing problems. Preferred modes and orders of surfactant addition are described hereinafter.
  • a detergent builder system comprising one or more non-phosphate detergent builders.
  • non-phosphate detergent builders can include, but are not restricted to alkali metal carbonates, bicarbonates, silicates, aluminosilicates, monomeric polycarboxylates, 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 than two carbon atoms, organic phosphonates and a inoalkylene poly (alkylene phosphonates) and mixtures of any of the foregoing.
  • the builder system is present in an amount of from 25% to 60% by weight of the composition, more preferably from 30% to 60% by weight.
  • Preferred builder systems are free of boron compounds and any polymeric organic materials are preferably biodegradable.
  • Suitable silicates are those having an Si ⁇ 2 :Na 2 0 ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of Si ⁇ 2 : Na 2 0 ratios from 2.0 to 2.8 being preferred. These materials can be added at various points of the manufacturing process, such as in a slurry of components that are spray dried or in the form of an aqueous solution serving as an agglomerating agent for other solid components, or, where the silicates are themselves in particulate form, as solids to the other particulate components of the compositon. However, for compositions in which the percentage of spray dried components is low i.e. 30%, it is preferred to include the amorphous silicate in the spray-dried components.
  • M is sodium or hydrogen
  • x is a number from 1.9 to
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the a , ⁇ , ⁇ and ⁇ forms of Na 2 Si2 ⁇ 5.
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • preferred sodium aluminosilicate zeolites have the unit cell formula
  • z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the above aluminosilicate ion exchange materials are further characterised by a particle size diameter of from
  • aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaC0 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CAC0 3 /litre/minute/ (g/litre) [2 grains Ca ++ / gallon/minute/gram/gallon) ] of aluminosilicate (anhydrous basis) , and which generally lies within the range of from 130 mg equivalent of CaC0 3 /litre/minute/ (gram/litre) [2 grains/gallon/minute/ (gram/gallon) ] to 390 mg equivalent of CaC0 3 /litre/minute/ (gram/litre) [6 grains/gallon/minute/ (gram/gallon) ] , based on calcium ion hardness.
  • Optimum alu inosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaC0 3 /litre/ minute/ (gram/litre) [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 materials, but are preferably synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985, " 9.
  • 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
  • x is from 20 to 30, especially 27.
  • Zeolite X of formula Na 86 [ (A10 2 ) 86 (Si0 ) 106 3 • 276 H 2° ⁇ s also suitable, as well as Zeolite HS of formula Na 6 [(A10 2 ) 6 (Si0 2 ) 6 ] 7.5 H 2 O).
  • Suitable water-soluble monomeric or oligomeric carboxylate builders include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, alonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • 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. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l, 1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No.
  • 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.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5- tetrahydrofuran - cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water-soluble organic salts are the 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 examples include p o l yacry l a t es o f M W t 2000-5000 and their copo l ymers wit h ma l e i c an h y d ri d e, such copolymers having a mo l ecu l ar we i ght of from 2 0 ,000 to 70,000, especially a b out 40 , 000 .
  • S uch bu i lder polymeric materials may be identical to the polymeric materials as binder materials and coating mater i als, as described hereinabove.
  • These materials are normally use d at levels of from 0.5% to 10 % by weight more pre f era b ly f rom 0 .75% to 8%, most prefera b ly from 1 % to 6 % b y weight of the composition.
  • Another preferred polycarboxylate b uilder is ethylenediamine-N,N.- d isuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDD S compoun d s are the free acid form an d the so d ium or magnesium salt thereof Pva «« ⁇ « ⁇ * salts o f ⁇ ⁇ • ' Examples of such Preferred sodium salts f EDD S i nclude NaEDDS, Na 2 EDD S an d Na 4 EDD S .
  • SUCh Preferred magnesium salts of EDDS include and Mg 2 EDD S .
  • the magnesium salts are the m ost preferre d for inclusion in compositions in accordance with the invention.
  • EDD S can be synthesised, for example, from readily ava i lable, inexpensive starting material such as maleic anhydride and ethylene diamine as follows •
  • the [ S , S ] isomer of EDDS can be synthesised from L- aspartic acid and 1, .2-dibromoethane, as follows :
  • Organic phosphonates and amino alkylene poly (alkylene phosphonates) include alkali metal ethane 1-hydroxy diphosphonates, nitrilo tri ethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates, although these materials are less preferred where the minimisation of phosphorus compounds in the compositions is desired.
  • the non-phosphate builder ingredient will comprise from 25% to 60% by weight of the compositions, more preferably from 30% to 60% by weight.
  • sodium aluminosilicate such as Zeolite A will comprise from 20% to 60% by weight of the total amount of builder
  • a monomeric or oligomeric carboxylate will comprise from 10% to 30% by weight of the total amount of builder
  • a crystalline layered silicate will comprise from 10% to 65% by weight of the total amount of builder.
  • the builder ingredient preferably also incorporates a combination of auxiliary inorganic and organic builders such as sodium carbonate and maleic anhydride/acrylic acid copolymers in amounts of up to 35% by weight of the total builder.
  • Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethycellulose, and ho o-or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • polyethylene glycols particularly those of molecular weight 1000- 10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co ⁇ polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4 ,4 1 -bis- (2-diethanolamino- 4-anilino -s- triazin-6- ylamino) stilbene-2:2 1 disulphonate, disodium 4 , 4 1 -bis-(2-morpholino -4-anilino- 2-triazin-6-ylaminostilbene-2:2 1 -disulphonate,disodium 4, 4 1 -bis-(2 , 4-dianilino-s-triazin-6-ylamino) stilbene-2:2 1 disulphonate, monosodium 4 1 '4 13 —bis-(2, 4-dianilino-s- triazin-6 ylamino) stilbene-2- sulphonate, disodium 4,4 ⁇ bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino) -2- triazin-6-ylamino) stilbene-2
  • Soil-release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particular preferred polymer in accordance with EP-A-0272033 has the formula
  • Certain polymeric materials such as polyvinyl pyrrolidones typically of MWt 5000-20000, preferably 10000-15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process.
  • Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica- silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
  • Other particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 0.5% by weight of the composition, preferably from 0.01% to 0.1% by weight.
  • the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
  • the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C 2Q -C 2 4 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix.
  • Other suds controlling materials such as C 2Q -C 2 4 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix.
  • Another optional ingredient useful in the present invention is one or more enzymes.
  • Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, upases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1,400,898. Organic fabric softening agents include the water- insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B- 0011340.
  • Levels of smectite clay are normally in the range from 5% to 15%, more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the high molecular weight polyethylene oxide materials and the water-soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.
  • coated peroxyacid bleach precursor particulates of the present invention are particularly useful in concentrated granular detergent compositions that are characterised by a relatively high density in comparison with conventional laundry detergent compositions.
  • Such high density compositions have a bulk density of at least 650 g/litre, more usually at least 700 g/litre and more preferably in excess of 800 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 and 40 mm at its respective upper and lower extremities. 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 e.g. a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide the bulk density in g/litre. Replicate measurements are made as required.
  • Concentrated detergent compositions also normally incorporate at least one multi-ingredient component i.e. they do not comprise compositions formed merely by dry- mixing individual ingredients. Compositions in which each individual ingredient is dry-mixed are generally dusty, slow to dissolve and also tend to cake and develop poor particle flow characteristics in storage.
  • compositions of the invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation and preferred methods involve combinations of these techniques.
  • a preferred method of making the compositions involves a combination of spray drying, agglomeration in a high speed mixer and dry mixing.
  • Preferred detergent compositions in accordance with the invention comprise at least two particulate multi- ingredient components.
  • the first component comprises at least 15%, conventionally from 25% to 50%, but more preferably no more than 35% by weight of the composition and the second component from 1% to 50%, more preferably 10% to 40% by weight of the composition.
  • the first component comprises a particulate incorporating an anionic surfactant in an amount of from 0.75% to 40% by weight of the powder and one or more inorganic and/or organic salts in an amount of from 99.25% to 60% by weight of the powder.
  • the particulate can have any suitable form such as granules, flakes, prills, marumes or noodles but is preferably granular.
  • the granules themselves may be agglomerates formed by pan or drum agglomeration or by in ⁇ line mixers but are customarily spray dried particles produced by atomising an aqueous slurry of the ingredients in a hot air stream which removes most of the water.
  • the spray dried granules are then subjected to densification steps, e.g. by high speed cutter mixers and/or compacting mills, to increase density before being reagglomerated.
  • densification steps e.g. by high speed cutter mixers and/or compacting mills
  • the first component is described hereinafter as a spray dried powder.
  • Suitable anionic surfactants for the purposes of the first component have been found to be slowly dissolving linear alkyl sulfate salts in which the alkyl group has an average of from 16 to 22 carbon atoms, and linear alkyl carboxylate salts in which the alkyl group has an average of from 16 to 24 carbon atoms.
  • the alkyl groups for both types of surfactant are preferably derived from natural sources such as tallow fat and marine oils.
  • the level of anionic surfactant in the spray dried powder forming the first component is from 0.75% to 40% by weight, more usually 2.5% to 25% preferably from 3% to 20% and most preferably from 5% to 15% by weight.
  • Water- soluble surfactants such as linear alkyl benzene sulphonates or C 14 -C 15 alkyl sulphates can be included or alternatively may be applied subsequently to the spray dried powder by spray on.
  • the other major ingredient of the spray dried powder is one or more inorganic or organic salts that provide the crystalline structure for the granules.
  • the inorganic and/or organic salts may be water-soluble or water- insoluble, the latter type being comprised by the, or the major part of the, water-insoluble builders where these form part of the builder ingredient.
  • Suitable water- soluble inorganic salts include the alkali metal carbonates and bicarbonates.
  • Alkali metal silicates other than crystalline layered silicates can also be present in the spray dried granule provided that aluminosilicate does not form part of the spray dried component.
  • water-soluble sulphate particularly sodium sulphate
  • water-soluble sulphate should not be present at a level of more than 2.5% by weight of the composition.
  • no sodium sulphate is added as a separate ingredient and its incorporation as a by-product e.g. with sulph(on)ated surfactants, should be minimised.
  • an aluminosilicate zeolite forms the, or part of the, builder ingredient, it is preferred that it is not added directly by dry-mixing to the other components, but is incorporated into the multi-ingredient component(s) .
  • any silicate present should not form part of the spray-dried granule.
  • incorporation of the silicate can be achieved in several ways, e.g. by producing a separate silicate-containing spray-dried particulate, by incorporating the silicate into an agglomerate of other ingredients, or more preferably by adding the silicate as a dry mixed solid ingredient.
  • the first component can also include up to 15% by weight of miscellaneous ingredients such as brighteners, anti- redepo ⁇ ition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and heavy metal sequestering agents.
  • miscellaneous ingredients such as brighteners, anti- redepo ⁇ ition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and heavy metal sequestering agents.
  • miscellaneous ingredients such as brighteners, anti- redepo ⁇ ition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and heavy metal sequestering agents.
  • the first component is a spray dried powder it will normally be dried to a moisture content of from 7% to 11% by weight, more preferably from 8% to 10% by weight of the spray dried powder.
  • Moisture contents of powders produced by other processes such as agglomeration may be lower and can be
  • the particle size of the first component is conventional and preferably not more than 5% by weight should be above 1.4mm, while not more than 10% by weight should be less than 0.15 mm in maximum dimension. Preferably at least 60%, and most preferably at least 80%, by weight of the powder lies between 0.7 mm and 0.25 mm in size.
  • the bulk density of the particles from the spray drying tower is conventionally in the range from 540 to 600 g/litre and this is then enhanced by further processing steps such as size reduction in a high speed cutter/mixer followed by compaction. Alternatively, processes other than spray drying may be used to form a high density particulate directly.
  • a second component of a preferred composition in accordance with the invention is another multi-ingredient particulate containing a water-soluble surfactant.
  • This may be anionic, nonionic, cationic or semipolar in type or a mixture of any of these.
  • Suitable surfactants are listed hereinbefore but preferred surfactants are C Q _ 4 -
  • the second component may have any suitable physical form, i.e. it - ay take the form of flakes, prills, marumes, noodles, ribbons, or granules which may be spray-dried or non spray-dried agglomerates.
  • the second component could in theory comprise the water-soluble surfactant on its own, in practice at least one organic or inorganic salt is included to facilitate processing. This provides a degree of crystallinity, and hence acceptable flow characteristics, to the particulate and may be any one or more of the organic or inorganic salts present in the first component.
  • the particle size range of the second component should be such as to obviate segregation from the particles of the first component when blended therewith. Thus not more than 5% by weight should be above 1.4 mm while not more than 10% should be less than 0.15 mm in maximum dimension.
  • the bulk density of the second component will be a function of its mode of preparation.
  • the preferred form of the second component is a mechanically mixed agglomerate which may be made by adding the ingredients dry or with an agglomerating agent to a pan agglomerator, Z blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050 F.R.G.
  • the second component can be given a bulk density in the range from 650 g/litre to 1190 g/litre more preferably from 750 g/litre to 850 g/litre.
  • compositions include a avel of alkali metal carbonate in the second compone corresponding to an amount of from 3% to 15% by eigh of the composition, more preferably from 5% to 1 % by weight. This will provide a level of carbonate in the second component of from 20% to 40% by weight.
  • a highly preferred ingredient of the second component is also a hydrated water-insoluble aluminosilicate ion exchange material of the synthetic zeolite type, described hereinbefore, present at from 10% to 35% by weight of the second component.
  • the amount of water-insoluble aluminosilicate material incorporated in this way is from 1% to 10% by weight of the composition, more preferably from 2% to 8% by weight.
  • the surfactant salt is formed in situ in an inline mixer.
  • the liquid acid form of the surfactant is added to a mixture of particulate anhydrous sodium carbonate and hydrated sodium aluminosilicate in a continuous high speed blender, such as a Lodige KM mixer, and neutralised to form the surfactant salt whilst maintaining the particulate nature of the mixture.
  • the resultant agglomerated mixture forms the second component which is then added to other components of the product.
  • the surfactant salt is pre-neutralised and added as a viscous paste to the mixture of the other ingredients.
  • the mixer serves merely to agglomerate the ingredients to form the second component.
  • part of the spray dried product comprising the first granular component is diverted and subjected to a low level of nonionic surfactant spray on before being reblended with the remainder.
  • the second granular component is made using the preferred process described above.
  • the first and second components together with the coated bleach precursor particulate and the perhydrate bleach, other dry mix ingredients such as any carboxylate chelating agent, soil-release polymer, silicate of conventional or crystalline layered type, and enzyme are then fed to a conveyor belt, from which they are transferred to a horizontally rotating drum in which perfume and silicone suds suppressor are sprayed on to the product.
  • a further drum mixing step is employed in which a low (approx. 2% by weight) level of finely divided crystalline material is introduced to increase density and improve granular flow characteristics.
  • compositions in accordance with the invention can also benefit from delivery systems that provide transient localised high concentrations of product in the drum of an automatic washing machine at the start of the wash cycle, thereby also avoiding problems associated with loss of product in the pipework or sump of the machine.
  • Delivery to the drum can most easily be achieved by incorporation of the composition in a bag or container from which it is rapidly releasable at the start of the wash cycle in response to agitation, a rise in temperature or immersion in the wash water in the drum.
  • the washing machine itself may be adapted to permit direct addition of the composition to the drum e.g. by a dispensing arrangement in the access door.
  • Products comprising a detergent composition enclosed in a bag or container are usually designed in such a way that container integrity is maintained in the dry state to prevent egress of the contents when dry, but are adapted for release of the container contents on exposure to a washing environment, normally on immersion in an aqueous solution.
  • the container will be flexible, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water-soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • laminated sheet products can be employed in which a central flexible layer is impregnated and/or coated with a composition and then one or more outer layers are applied to produce a fabric ⁇ like aesthetic effect.
  • the layers may be sealed together so as to remain attached during use or may separate on contact with water to facilitate the release of the coated or impregnated material.
  • An alternative laminate form comprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the detergent components are deposited in measured amounts, with a second layer overlying the first layer and sealed thereto in those areas beteen the pouch-like containers where the two layers are in contact.
  • the components may be deposited in particulate, paste or molten form and the laminate layers should prevent egress of the contents of the pouch-like containers prior to their addition to water.
  • the layers may separate or may remain attached together on contact with water, the only requirement being that the structure should permit rapid release of the contents of the pouch-like containers into solution.
  • the number of pouch-like containers per unit area of substrate is a matter of choice but will normally vary between 500 and 25,000 per square metre.
  • Suitable materials which can be used for the flexible laminate layers in this aspect of the invention include, among others, sponges, paper and woven and non-woven fabrics.
  • the preferred means of carrying out the process of the invention is to introduce the composition into the liquid surrounding the fabrics that are in the drum via a reusable dispensing device having walls that are permeable to liquid but impermeable to the solid composition.
  • the support ring is provided with a masking arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
  • Tetra Acetyl Ethylene Diamine in fine powder form (purity ca 99.0%, particle size 90% by weight less than 150 micrometers) was agglomerated with a 40% aqueous solution of Sokalan (R) CP45 at a binder level of 24% (by weight) .
  • the agglomeration was carried out in a plough ⁇ share mixer and the resultant, wet, agglomerate was then dried in a fluid-bed dryer.
  • the agglomerate was then spray-coated with a further quantitiy (12.5% by weight) of the said polymer solution.
  • the coated agglomerate was then dried again using a fluid-bed and screened to provide a finished material with particle size where more than 90% lay between 425 micrometers and 1700 micrometers.
  • composition of the final agglomerate was as follows : TAED 82.0%
  • a reference TAED agglomerate was prepared by agglomerating the same TAED powder with molten TAE25 as binder in the same mixing device as above. Particles were then cooled and sized to the same standards as above. Agglomerate composition was :
  • the detergent agglomerates were tested for colour damage potential when incorporated into the following detergent matrix (composition in parts by weight) :
  • Silicate (Si02:Na20 2:1) 3.5
  • the detergent matrix already contains Sokalan (R) CP45 as a co-builder, independently from the Sokalan (R) CP45 present in the agglomerates.
  • the amount of agglomerate in the composition was such as to provide an active level of 5% by weight of TAED versus the total composition.
  • the formulations containing the TAED agglomerates were subjected to a full scale washing machine test using Miele automatic washing machines (Model W754) set to the Short Wash cycle at 40°C.
  • Bi ch-sensitive coloured fabric swatches were used, a 43 cm2 swatch being wrapped around the dispensing device in which lOOg of the formulation was added.
  • 3.3 kg of white cotton bedsheets were used as ballast.
  • 12 litres of water of 150 ppm hardness (expressed as CaC ⁇ 3 ) with a Ca:Mg ratio of 3:1 was fed to each machine.
  • the swatches were made of 100% lambswool woven fabric with purple 48 dye (Design No. W3970) supplied by Borval Fabrics, Albert Street, Huddersfield, West Yorkshire, England. 24 replicates of each treatment were performed and the swatches were then graded visually for fabric colour damage by an expert panel using the following grading system.
  • Tetra acetyl Ethylene Diamine (TAED) in fine powder form (purity ca. 99.0%) and particle size 90% by weight less than 150 micrometers was agglomerated with a 40 % aqueous solution of Sokalan(R) CP45 at a binder level of 24% by weight.
  • the agglomeration was carried out in Lodige high shear mixer and the resultant moist agglomerate was then dried in a fluid-bed to a residual moisture content of less than 10%.
  • the agglomerate was then spray-coated with a further quantity of Sokalan (R) CP45 (25.0% by weight) in a Lodige plough-share mixer and again the moist agglomerate dried in a fluid-bed to a residual moisture content of less than 5% ( by weight) .
  • the agglomerate was then screened to provide a finished agglomerate where 85% by weight lay between 1700 micrometers and 425 micron.
  • composition of the final agglomerate was:
  • the mean coating level of the composition which was determined by acid-base titration and calculation of the difference, was 9.1%. Using sieves, the composition was then separated into four classes of particles. In each class, the mean coating level was determined by acid-base tritration and calculation of the difference.
  • the mean coating distribution was as follows:
  • composition according to this example was evaluated as in example 1. Results were:
  • compositions of the present invention also provided superior bleaching.

Abstract

L'invention se rapporte à une composition de précurseur de blanchiment à base de peroxyacide solide, qui comprend des particules d'un précurseur de blanchiment à base de peroxyacide enrobé d'une substance choisie parmi des polymères acides solubles dans l'eau.
PCT/US1993/006801 1992-08-01 1993-07-20 Compositions de precurseurs de blanchiment a base de peroxyacide WO1994003395A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU47770/93A AU4777093A (en) 1992-08-01 1993-07-20 Peroxyacid bleach precursor compositions
JP6505341A JPH09502208A (ja) 1992-12-22 1993-07-20 ペルオキシ酸漂白剤前駆物質組成物
EP93918259A EP0652848A4 (fr) 1992-08-01 1993-07-20 Compositions de precurseurs de blanchiment a base de peroxyacide.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP92202388 1992-08-01
EP92202388.2 1992-08-01
EP92204061.3 1992-12-22
EP92204061 1992-12-22

Publications (1)

Publication Number Publication Date
WO1994003395A1 true WO1994003395A1 (fr) 1994-02-17

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Application Number Title Priority Date Filing Date
PCT/US1993/006801 WO1994003395A1 (fr) 1992-08-01 1993-07-20 Compositions de precurseurs de blanchiment a base de peroxyacide

Country Status (8)

Country Link
CN (1) CN1084883A (fr)
AU (1) AU4777093A (fr)
CA (1) CA2141586A1 (fr)
MA (1) MA22946A1 (fr)
MX (1) MX9304667A (fr)
TR (1) TR27734A (fr)
TW (1) TW230221B (fr)
WO (1) WO1994003395A1 (fr)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0710716A2 (fr) 1994-11-02 1996-05-08 Hoechst Aktiengesellschaft Activateurs de blanchiment sous forme granulaire et leur production
EP0985728A1 (fr) * 1998-09-09 2000-03-15 Clariant GmbH Activateur de blanchiment en forme granulaire
US6270690B1 (en) 1997-09-16 2001-08-07 Clariant Gmbh Storage stable bleach activator granules
DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9518013B2 (en) 2014-12-18 2016-12-13 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
WO2018095956A1 (fr) * 2016-11-25 2018-05-31 Henkel Ag & Co. Kgaa Sachet contenant un mélange activateur de blanchiment/agent complexant
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment

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DE3826092A1 (de) * 1988-08-01 1990-02-08 Henkel Kgaa Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel mit verbesserten eigenschaften
US4997590A (en) * 1988-12-22 1991-03-05 The Procter & Gamble Company Process of coloring stabilized bleach activator extrudates
GB8902909D0 (en) * 1989-02-09 1989-03-30 Unilever Plc Coating process
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US4921631A (en) * 1987-05-12 1990-05-01 Warwick International Limited Bleach activator compositions
US4759956A (en) * 1987-05-22 1988-07-26 Lever Brothers Company Process for encapsulating particles using polymer latex
US5100576A (en) * 1988-12-22 1992-03-31 Hoechst Aktiengesellschaft Process for the preparation of a readily soluble bleach activator granulate with a long shelf life
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Cited By (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0710716A2 (fr) 1994-11-02 1996-05-08 Hoechst Aktiengesellschaft Activateurs de blanchiment sous forme granulaire et leur production
US5716569A (en) * 1994-11-02 1998-02-10 Hoechst Aktiengesellschaft Granulated bleaching activators and their preparation
US6270690B1 (en) 1997-09-16 2001-08-07 Clariant Gmbh Storage stable bleach activator granules
EP0985728A1 (fr) * 1998-09-09 2000-03-15 Clariant GmbH Activateur de blanchiment en forme granulaire
US6214785B1 (en) 1998-09-09 2001-04-10 Clariant Gmbh Bleach activator granules
DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
US10323218B2 (en) 2008-03-28 2019-06-18 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11827867B2 (en) 2008-03-28 2023-11-28 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10077415B2 (en) 2008-03-28 2018-09-18 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10669512B2 (en) 2008-03-28 2020-06-02 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11015151B2 (en) 2008-03-28 2021-05-25 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9359295B2 (en) 2008-03-28 2016-06-07 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10017720B2 (en) 2008-03-28 2018-07-10 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US8858895B2 (en) 2010-12-29 2014-10-14 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US8877254B2 (en) 2010-12-29 2014-11-04 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US11678664B2 (en) 2010-12-29 2023-06-20 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US9365509B2 (en) 2010-12-29 2016-06-14 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9505715B2 (en) 2010-12-29 2016-11-29 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US11311011B2 (en) 2010-12-29 2022-04-26 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9192909B2 (en) 2010-12-29 2015-11-24 Ecolab USA, Inc. Sugar ester peracid on site generator and formulator
US8933263B2 (en) 2010-12-29 2015-01-13 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US11330818B2 (en) 2010-12-29 2022-05-17 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US10477862B2 (en) 2010-12-29 2019-11-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US9861101B2 (en) 2010-12-29 2018-01-09 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US9883672B2 (en) 2010-12-29 2018-02-06 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US10244751B2 (en) 2010-12-29 2019-04-02 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US10201156B2 (en) 2010-12-29 2019-02-12 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
US10010075B2 (en) 2010-12-29 2018-07-03 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9585397B2 (en) 2013-03-05 2017-03-07 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9675076B2 (en) 2013-03-05 2017-06-13 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11026421B2 (en) 2013-03-05 2021-06-08 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10433547B2 (en) 2014-12-18 2019-10-08 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9518013B2 (en) 2014-12-18 2016-12-13 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US10834924B2 (en) 2014-12-18 2020-11-17 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US10709131B2 (en) 2014-12-18 2020-07-14 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US10233149B2 (en) 2014-12-18 2019-03-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US11772998B2 (en) 2014-12-18 2023-10-03 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US10899707B2 (en) 2014-12-18 2021-01-26 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US11325887B2 (en) 2014-12-18 2022-05-10 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US10542751B2 (en) 2014-12-18 2020-01-28 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US11684067B2 (en) 2014-12-18 2023-06-27 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US11220660B2 (en) 2016-11-25 2022-01-11 Henkel Ag & Co. Kgaa Portion bag having bleach activator/complexing agent compound
WO2018095956A1 (fr) * 2016-11-25 2018-05-31 Henkel Ag & Co. Kgaa Sachet contenant un mélange activateur de blanchiment/agent complexant
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment
US11771673B2 (en) 2018-06-15 2023-10-03 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment

Also Published As

Publication number Publication date
TR27734A (tr) 1995-07-07
MA22946A1 (fr) 1994-04-01
CA2141586A1 (fr) 1994-02-17
TW230221B (fr) 1994-09-11
MX9304667A (es) 1994-03-31
CN1084883A (zh) 1994-04-06
AU4777093A (en) 1994-03-03

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