WO1996016148A1 - Compositions de precurseurs de blanchiment a base de peroxyacide hydrophobe stabilisees par un acide carboxylique hydrosoluble - Google Patents

Compositions de precurseurs de blanchiment a base de peroxyacide hydrophobe stabilisees par un acide carboxylique hydrosoluble Download PDF

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Publication number
WO1996016148A1
WO1996016148A1 PCT/US1995/015494 US9515494W WO9616148A1 WO 1996016148 A1 WO1996016148 A1 WO 1996016148A1 US 9515494 W US9515494 W US 9515494W WO 9616148 A1 WO9616148 A1 WO 9616148A1
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Prior art keywords
bleach precursor
peroxyacid
peroxyacid bleach
precursor composition
composition according
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PCT/US1995/015494
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English (en)
Inventor
Nour-Eddine Guedira
Richard Timothy Hartshorn
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to DE69530783T priority Critical patent/DE69530783T2/de
Priority to EP95940865A priority patent/EP0791044B1/fr
Priority to MX9703683A priority patent/MX9703683A/es
Priority to CA002204153A priority patent/CA2204153C/fr
Priority to BR9510356A priority patent/BR9510356A/pt
Priority to AT95940865T priority patent/ATE240382T1/de
Publication of WO1996016148A1 publication Critical patent/WO1996016148A1/fr
Anticipated expiration legal-status Critical
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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

  • the present invention relates to peroxyacid bleach precursor compositions and to detergent compositions containing them, which have improved perhydrolysis rate as well as improved storage stability. More particularly, it relates to bleach activators which in aqueous media produce hydrophobic peroxyacids.
  • bleach activators are susceptible to hydrolysis under alkaline conditions, which thus reduces the storage stability as well as the perhydrolysis rate when in aqueous wash liquor.
  • the prior art contains numerous examples of organic peroxyacid bleach precursors 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 organic peroxyacid bleach precursors prepared by spray drying an aqueous pumpable dispersion containing an N-acyl or O-acyl compound together with at least one water soluble cellulo ⁇ e 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 organic peroxyacid bleach precursors with a mixture of alkali metal Cg - C 2 fetty acid salts in admixture with the corresponding fatty acids.
  • GB-A- 1381121 employs a molten coating of inter alia C14 - Cjg fatty acid mixtures to protect solid organic peroxyacid bleach precursors.
  • GB-A-1441416 discloses a similar process employing a mixture of Cj2 - C14 fatty acids and C10 - C20 aliphatic alcohols.
  • EP-A-0375241 describes stabilised organic peroxyacid bleach precursor extrudates in which C5- Cig 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 organic peroxyacid bleach precursor, a water soluble film forming polymer and 2-15% of a C3-C6 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 organic peroxyacid bleach precursor and then granulated with the film forming polymer.
  • a granule comprising 88.1 % of TAED of mean particle size of 0.01 to 0.8mm, 10.4% of citric acid, 0.5% polyacrylate and 1.0% of water.
  • the citric acid is asserted to provide an enhanced rate of dissolution of the organic peroxyacid bleach precursor granules.
  • EP-A-0382464 concerns a process for coating or encapsulation of solid particles including bleaching compounds and organic peroxyacid bleach precursors 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 paniculate 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.
  • caproyl oxybenzene sulfonate such as (6- octanamido-caproyl)oxybenzenesulfonate , (6-nonanamidocaproy l)oxy benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof are used, the Applicants have found that these problems were exacerbated.
  • a peroxyacid bleach precursor composition comprising: a)-a paniculate peroxyacid bleach precursor of a size less than lOO ⁇ m and selected from precursors which produce under perhydrolysis hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than
  • the term close physical proximity means one of the following: i) an agglomerate or extrudate in which said precursor and said organic acid are in intimate admixture; ii) a bleach precursor paniculate coated with one or more layers wherein at least one layer contains the organic acid; iii) an organic acid compound coated with one or more layers wherein at least one layer contains the bleach activator.
  • An essential feature of the invention is a peroxyacid bleach precursor which produces upon perhydrolysis hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 20°-50°C.
  • the peroxyacid backbone chain contains at least 7 carbons which may be partly or totally branched, chained or cyclic and any mixtures thereof.
  • 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 peroxyacid bleach precursor for the purpose of the invention are the amide substituted compounds of the following general formulae:
  • Rl is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from about 6 to 12 carbon atoms.
  • R2 preferably contains from about 4 to 8 carbon atoms.
  • R may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R ⁇ .
  • R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in 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 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • 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 -1" , -CC ⁇ ' M , -SO ⁇ ' M + , -N + (R 3 ) X " and 0 ⁇ -N(R 3 ) 3 and most preferably -SC ⁇ M "1" and -C ⁇ 2 ⁇ M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • bleach activators of the above formulae include derivatives of caproyl oxybenzene sulfonate selected from (6-octanamido- caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sul ⁇ fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in EP-A-0170386.
  • Still another preferred class of bleach activator is the class of alkyl percarboxylic acid bleach precursors.
  • Preferred alkyl percarboxylic acid precursors include nonanoyl oxy benzene sulphonate (NOBS described in US 4,412,934) and 3,5,5-tri- methyl hexanoyl oxybenzene sulfonate (ISONOBS described in EP120,591) and salts thereof.
  • the peroxyacid bleach precursors are normally incorporated at a level of from 20% to 95% by weight of the bleach precursor composition, preferably at least 50% and most preferably at least 60% by weight thereof.
  • the peroxyacid bleach precursor is typically from 1 % to 20% by weight, more preferably from 1 % to 10% by weight, most preferably from 1 % to 7% by weight of the detergent compositions.
  • composition of the invention contains as another essential component a water-soluble organic acid compound.
  • Organic acids compounds suitable for incorporation as agglomerating agents of the particles of the invention comprise aliphatic or aromatic carboxylates.
  • the carboxylates may be monomeric, oligomeric or polymeric in nature and preferably comprise aliphatic carboxylic acids.
  • monomeric aliphatic acid compounds are glycolic, glutamic, citraconic, succinic, 1 -lactic, malonic, glutaric, adipic, maleic, malic, tartaric, citric, diglycolic and carboxymethyl succinic acids.
  • polymeric acid compounds include poly(meth)acrylic acids and copolymeric derivatives with maleic anhydride.
  • the organic acid is a monomeric or oligomeric carboxylate and more preferably a monomeric aliphatic carboxylic acid.
  • Preferred monomeric aliphatic acids are 1 -lactic, citric and glycolic acids while preferred polymeric acids include polyacrylic acids of MWt 3000-5000, especially about 4500 and acrylic acid maleic anhydride copolymers of MWt 40,000-90,000.
  • a preferred organic acid is citric acid.
  • the organic acid is incorporated at levels of from 5% to 50% by weight of the paniculate to be agglomerated, more preferably from 5% to 25% by weight and most preferably from 7% to 20% by weight.
  • agglomerates may require the addition of one or more binder agents in order to assist in binding the organic peroxyacid bleach precursor compound and organic acid compound so as to produce particulates with acceptable physical characteristics.
  • the binder agents may be present at a level of from 0% to 40% by weight of the particulate.
  • the binder agents will be in intimate admixture with the organic peroxyacid bleach precursor compound and organic acid compound.
  • Preferred binder agents have a melting point between 30°C-70°C.
  • the binder agents are preferably present in amounts from 1-30% by weight of the particulate and most preferably from 2-20% by weight of the particulate.
  • Preferred binder agents include the C10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol. Of these tallow alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) are preferred.
  • binder agents include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols with an average weight of from 600 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid are further examples of polymeric materials useful as binder agents. Of these, copolymers of maleic anhydride with acrylic acid are preferred.
  • These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole.
  • Further examples of binder agents include the C ⁇ o -C20 mono- and diglycerol ethers and also the C10-C20 fetty acids. Solutions of certain inorganic salts including sodium silicate are also of use for this purpose.
  • Cellulose derivatives such as carboxymethylcellulose, and homo- or co ⁇ polymeric polycarboxylic acid or their salts are other examples of suitable binder agents.
  • additives that are compatible with the peroxyacid precursors may also be included in detergent additive compositions in accordance with the invention.
  • additives include surfactants, fluorescers, enzymes, suds suppressors, dye transfer inhibition agents, soil suspending agents, water soluble builders and chelating agents. Specific embodiments of such additives and their levels of incorporation are described hereinafter but the total level of the additives normally lies in the range of from 5% to 50% by weight of the additive composition.
  • the peroxyacid precursor(s) should substantially form the major component of the precursor composition, ie. from 20% to 95% by weight of the agglomerate, preferably at least 50% by weight and most preferably at least 60% by weight thereof.
  • the diameter of the pores forming the spaces between the agglomerated particles is selected by controlling the levels of compaction and shear applied during the agglomeration process. Too large a pore size results in an agglomerate of inadequate strength and a tendency to disintegrate during handling. Too small a pore size results in an agglomerate having a slow rate of dissolution. It has been found that a satisfactory agglomerate has a % of porosity of at least 12 corresponding to a mean pore diameter of at least 0.5 ⁇ m and preferably in the range of from 0.6 to 5 micrometers. The porosity is measured according to the following technique, using a Micromeritics Poresizer 9320.
  • This equipment is manufactured by Micromeritics Instrument Corporation, One Micromeritics Drive, Norcross GA 30093-1877, USA and comprises a Penetrometer, Analyser and printer.
  • the Penetrometer bulb is filled with a known weight (to 4dp) of particulate material.
  • the Penetrometer is then fully assembled with the insulator seal, spring and retaining collar. This is then fitted into the low pressure port of the porosity analyser.
  • the Penetrometer is then evacuated and the sample analysed under the following set point conditions:
  • the Penetrometer bulb is installed in the high pressure chamber and analysed under the same set point conditions and the printer then gives the median pore diameter and pore intrusion volumes for the sample.
  • the pore intrusion volume is at least 0.2 ml/g
  • Detergent compositions incorporating the peroxy acid bleach precursor particulates will normally contain from 1 % to 20% of the precursor, more frequently from 1 % to 10% and most preferably from 1 % to 7%, 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.
  • additional components and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • compositions of the invention may, for example, be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in the pretreatment of stained fabrics and machine dishwashing compositions.
  • compositions suitable for use in a machine washing method eg: machine laundry and machine dishwashing methods
  • the compositions of the invention preferably contain one or more additional detersive components.
  • 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 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 40% by weight, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition.
  • T e perhydrate may be any of the alkalimetal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate.
  • Sodium percarbonate which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 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.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate
  • 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 variety of coatings can be used including borate, boric acid and citrate or sodium silicate of Si ⁇ 2:Na2 ⁇ 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.
  • the most preferred coating is a mixture of sodium carbonate and sulphate or sodium chloride.
  • the particle size range of the crystalline percarbonate is from 350 micrometers to 1500 micrometers with a mean of approximately 500-1000 micrometers.
  • a wide range of surfactants can be used in the detergent compositions.
  • a list of suitable cationic surfactants is given in USP 4,259,217 issued to Murphy on March 31, 1981.
  • Nonlimiting examples of surfactants useful herein typically at levels from 1 % to 55%, by weight include the conventional Cu-Ci8 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2) x (CHOS ⁇ 3 " M + ) CH3 and CH3 (CH2) y (CHOS ⁇ 3 " M “ “ ) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C ⁇ o ⁇ Cl8 alkyl alkoxy sulfates (“AE X S”; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxy lates (especially ethoxylates and mixed ethoxy /propoxy), C12-CI8 betaines and sulfobetaines ("sultaines"), C ⁇ o ⁇ C ⁇ g amine oxides, and the like, can also be included in the overall compositions.
  • the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-CI8 N- me hy lgluc amides.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as O-CJS (3-methoxypropyl) glucamide.
  • O-CJS 3-methoxypropyl
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10- C16 soaps may be used.
  • Suitable surfactants suitable for the purpose of the invention are the anionic alkali metal sarcosinates of formula: wherein R is a C9-C17 linear or branched alkyl or alkenyl group, R is a C1-C4 alkyl group and N is an alkali metal ion.
  • R is a C9-C17 linear or branched alkyl or alkenyl group
  • R is a C1-C4 alkyl group
  • N is an alkali metal ion.
  • Preferred examples are the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • compositions herein can optionally include one or more other additional detergent compounds or other compounds for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • additional detergent compounds e.g., perfumes, colorants, dyes, etc.
  • the following are illustrative examples of such additional detergent compounds.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder. Liquid formulations typically comprise from 5% to 50%, more typically 5% to 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates). Non-phosphate builders may also be used.
  • polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates).
  • compositions herein function surprisingly well even in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the so called 'amorphous' alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Na SKS-6 silicate builder does not contain aluminium.
  • NaSKS-6 has the delta- Na2Si2 ⁇ 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3 ,417,649 and DE-A- 3,742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 + l*yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • the delta-Na2Si2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether poly carboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071.
  • Suitable ether poly carboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid, and carboxymethyloxysuccinic acid
  • poly acetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxyIic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
  • Fatty acids e.g., C12-C18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 -hydroxy- 1,1- diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, poly functionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates , N-hydroxyethy lethy lenediaminetriacetates , nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra- aminehexacetates, diethylenetriammepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Poly functionally- substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3 ,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233
  • EDDG ethylenediamine-N,N'-diglutamate
  • HPDDS 2-hydroxypropylene-diamine-N,N'-disuccinate
  • these chelating agents will generally comprise from 0.1 % to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1 % to 3.0% by weight of such compositions.
  • compositions according to the present invention can also optionally contain water- soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01% to 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 111,965. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 111 ,984; the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. Patent 4,548,744. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1- 3 vinyl esters, preferably poly (vinyl acetate) grafted onto poly alkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048).
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays and U.S. Patent 3,893,929.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sul- foarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy- 1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinyl imidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures:
  • Rj, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are poly vinyls, polyalkylenes, polyesters, poly ethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1 ,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinyl- pyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, mo hilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 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.
  • 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.
  • Rj is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6- morphilino-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.
  • optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • selected polymeric materials e.g., PVNO and/or PVPVI
  • selected optical brighteners e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX
  • Tinopal UNPA-GX Tinopal UNPA-GX
  • Tinopal 5BM-GX Tinopal 5BM-GX
  • Tinopal AMS-GX Tinopal AMS-GX
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.05% to 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[l,2-d]triazoles; 4,4'-bis- (1,2,3- triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4- methyl-7-diethyl- amino coumarin; l,2-bis(-venzimidazol-2-yl)ethylene; 1 ,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thio ⁇ hene; 2-stryl- napth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015. Anionic brighteners are preferred herein.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347.
  • the monocarboxylic fatty acids and salts thereof used 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.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc.
  • suds inhibitors include 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, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilise waxy hydrocarbons, preferably having a melting point below 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779 and EP 354016.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1,500 cs. at 25°C;
  • siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO ⁇ /2 units and to Si ⁇ 2 units of from 0.6:1 to 1.2:1;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b)
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight % , preferably more than 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glyco copolymer of polyethylene- polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C6-Ci6 alkyl alcohols having a Cj-Ci6 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to 5%, by weight, of the detergent composition.
  • from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01 % to 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • 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, lipases, peroxidases, esterases and cellulases conventionally incorporated into detergent compositions.
  • Suitable proteolytic enzymes are described in GB-A- 1243784, EP-A- 0130756 and USP 5185250 and 5204015.
  • Suitable amylases are disclosed in GB-A-1296839 while cellulases are disclosed in USP 4435307, GB-A- 2075028 and 2095275.
  • Lipases for use in detergent compositions are disclosed in GB-A-1372034 and EP-A-0341947.
  • a suitable peroxidase is disclosed by WO89/099813.
  • a wide range of enzyme materials and means for their incorporation into synthetic detergent granules is also discussed in US Patents 3,519,570 and 3,533,139.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416 and U.S. Patent 4,291,071.
  • compositions herein A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the ClO ⁇ Cl6 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgC , M SO and the like, can be added at levels of, typically, 0.1 %-2%, to provide additional suds and to enhance grease removal performance.
  • Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3% -5% of C 13.15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 ethoxylated alcohol
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3- ⁇ ropanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between 6.8 and 9.0.
  • Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the bulk density of granular detergent compositions is typically at least 450 g/litre, more usually at least 600 g/litre and more preferably from 650 g/litre to 1000 g/litre.
  • the invention is illustrated in the following non limiting examples, in which all percentages are on a weight basis unless otherwise stated.
  • MA/AA Copolymer of 1:4 maleic/acrylic acid average molecular weight about 70,000.
  • DETPMP Diethylene triamine penta (Methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060
  • a blend of (6-octanamido-caproyl) oxybenzenesulfonate/ (6-decanamido- caproyl) oxybenzenesulfonate in fine powder form (particle size less than 100 micrometers) and citric acid were added to the Kenwood food mixer and pre-mixed.
  • the temperature of the powders was 25 °C.
  • the molten nonionic binder TAE25 was added to the powder mix over a period of 2 minutes.
  • the resulting mass was further mixed for 30 seconds.
  • the mixing was then stopped and the agglomerate removed from the Kenwood food mixer and cooled to ambient temperature.
  • the product was then sieved and materials that were greater than 1180 micrometers and smaller than 250 micrometers were removed.
  • unrestrained dissolution conditions are defined as those existing in the Beaker Perhydrolysis Test as carried out using a Sotax Dissolution Tester Model AT6 supplied by Sotax AG CH-4008 BASEL Switzerland.
  • This Apparatus comprises an array of polycarbonate beakers, each capable of holding 1 litre of water, supported in a thermostatically controlled water bath. Each beaker is provided with a paddle stirrer whose speed can be controlled.
  • Material from each example was then incorporated into a model detergent formulation having the composition in % by weight.
  • (6-decanamido-caproyl) oxybenzenesulfonate in agglomerate form affords a way of improving the perhydrolysis versus (6- decanamido-caproyl) oxybenzenesulfonate in raw material form. Furthermore, it can also be seen that (6-decanamido-caproyl) oxybenzenesulfonate particles having a % of porosity > 12 and a mean pore diameter >0.5 ⁇ m show enhanced perhydrolysis.

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Abstract

La présente invention concerne une composition de précurseur au peroxyacide, ainsi qu'une composition détergente la renfermant. La composition de l'invention se compose: a) d'un précurseur de blanchiment particulaire à base de peroxyacide d'un calibre inférieur à 100νm, appartenant au groupe constitué des précurseurs produisant, sous perhydrolyse, un peroxyacide hydrophobe dont l'acide carboxylique parent présente une concentration micellaire critique inférieure à 0,5 moles/litre, et b) d'un composé d'acide organique hydrosoluble, ledit précurseur et ledit acide organique étant très proches physiquement. Les compositions de l'invention présentent une meilleure stabilité au stockage et un rendement accru de perhydrolyse.
PCT/US1995/015494 1994-11-19 1995-11-14 Compositions de precurseurs de blanchiment a base de peroxyacide hydrophobe stabilisees par un acide carboxylique hydrosoluble Ceased WO1996016148A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE69530783T DE69530783T2 (de) 1994-11-19 1995-11-14 Durch wasserlösliche carbonsäure stabilisierte peroxycarbonsäurebleichmittelvorstufen
EP95940865A EP0791044B1 (fr) 1994-11-19 1995-11-14 Compositions de precurseurs de blanchiment a base de peroxyacide hydrophobe stabilisees par un acide carboxylique hydrosoluble
MX9703683A MX9703683A (es) 1994-11-19 1995-11-14 Composiciones de precursor de blanqueo de peroxiacido hidrofobicas estabilizadas con un acido caboxilico soluble en agua.
CA002204153A CA2204153C (fr) 1994-11-19 1995-11-14 Compositions de precurseurs de blanchiment a base de peroxyacide hydrophobe stabilisees par un acide carboxylique hydrosoluble
BR9510356A BR9510356A (pt) 1994-11-19 1995-11-14 Composições precursoras de branqueamento de peroxiácido hidrófobas estabilizadas com um ácido carboxílico solúvel em água
AT95940865T ATE240382T1 (de) 1994-11-19 1995-11-14 Durch wasserlösliche carbonsäure stabilisierte peroxycarbonsäurebleichmittelvorstufen

Applications Claiming Priority (2)

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GB9423374.9 1994-11-19
GB9423374A GB9423374D0 (en) 1994-11-19 1994-11-19 Peroxyacid bleach precursor compositions

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WO1996016148A1 true WO1996016148A1 (fr) 1996-05-30

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AR (1) AR000157A1 (fr)
AT (1) ATE240382T1 (fr)
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CA (1) CA2204153C (fr)
DE (1) DE69530783T2 (fr)
ES (1) ES2194929T3 (fr)
GB (1) GB9423374D0 (fr)
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EP0816481A3 (fr) * 1996-06-26 1999-02-10 Unilever N.V. Granulés peracides contenant l'acide citrique de monohydrate pour l'amélioration de la vitesse de dissolution
US6200944B1 (en) * 1996-06-28 2001-03-13 The Procter & Gamble Company Bleach precursor compositions
US6498124B2 (en) 2000-06-02 2002-12-24 Eastman Chemical Company Isolation of phenyl ester salts from mixtures comprising sulfolane
US6497644B2 (en) 2000-06-02 2002-12-24 Eastman Chemical Company Process for recycling amido-carboxylic acid esters into amino-carboxylic acids
US6500973B2 (en) 2000-06-02 2002-12-31 Eastman Chemical Company Extractive solution crystallization of chemical compounds
US6527690B2 (en) 2000-06-02 2003-03-04 Bhaskar Krishna Arumugam Purification of phenyl ester salts
US6660712B2 (en) 2000-06-02 2003-12-09 Dale Elbert Van Sickle Stabilization of amido acids with antioxidants
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
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
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions
US12558713B2 (en) 2019-05-31 2026-02-24 Ecolab Usa Inc. Peracid compositions with conductivity monitoring capability

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US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
EP0318470A2 (fr) * 1987-07-08 1989-05-31 Warwick International Group Plc Composition de blanchissage et procédé pour son obtention
US5411673A (en) * 1991-02-06 1995-05-02 The Procter & Gamble Company Peroxyacid bleach precursor compositions
EP0598170A1 (fr) * 1992-11-16 1994-05-25 The Procter & Gamble Company Compositions de nettoyage et de blanchiment

Cited By (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0816481A3 (fr) * 1996-06-26 1999-02-10 Unilever N.V. Granulés peracides contenant l'acide citrique de monohydrate pour l'amélioration de la vitesse de dissolution
US6200944B1 (en) * 1996-06-28 2001-03-13 The Procter & Gamble Company Bleach precursor compositions
US6498124B2 (en) 2000-06-02 2002-12-24 Eastman Chemical Company Isolation of phenyl ester salts from mixtures comprising sulfolane
US6497644B2 (en) 2000-06-02 2002-12-24 Eastman Chemical Company Process for recycling amido-carboxylic acid esters into amino-carboxylic acids
US6500973B2 (en) 2000-06-02 2002-12-31 Eastman Chemical Company Extractive solution crystallization of chemical compounds
US6527690B2 (en) 2000-06-02 2003-03-04 Bhaskar Krishna Arumugam Purification of phenyl ester salts
US6660712B2 (en) 2000-06-02 2003-12-09 Dale Elbert Van Sickle Stabilization of amido acids with antioxidants
US6800771B2 (en) 2000-06-02 2004-10-05 Dale Elbert Van Sickle Stabilization of amido acids with antioxidants
US10077415B2 (en) 2008-03-28 2018-09-18 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US10323218B2 (en) 2008-03-28 2019-06-18 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
US10017720B2 (en) 2008-03-28 2018-07-10 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
US9676711B2 (en) 2008-03-28 2017-06-13 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
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US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US12114656B2 (en) 2010-12-29 2024-10-15 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
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US9192909B2 (en) 2010-12-29 2015-11-24 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
US8933263B2 (en) 2010-12-29 2015-01-13 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
US11311011B2 (en) 2010-12-29 2022-04-26 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
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
US10244751B2 (en) 2010-12-29 2019-04-02 Ecolab Usa Inc. Water temperature as a means of controlling kinetics of onsite generated peracids
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
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
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US8858895B2 (en) 2010-12-29 2014-10-14 Ecolab Usa Inc. Continuous on-line adjustable disinfectant/sanitizer/bleach generator
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US12593842B2 (en) 2010-12-29 2026-04-07 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
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
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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
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
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US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
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Also Published As

Publication number Publication date
DE69530783T2 (de) 2004-03-18
ATE240382T1 (de) 2003-05-15
EP0791044B1 (fr) 2003-05-14
CA2204153A1 (fr) 1996-05-30
CA2204153C (fr) 2001-07-10
GB9423374D0 (en) 1995-01-11
AR000157A1 (es) 1997-05-21
EP0791044A1 (fr) 1997-08-27
EP0791044A4 (fr) 1998-09-02
BR9510356A (pt) 1997-12-23
ES2194929T3 (es) 2003-12-01
DE69530783D1 (de) 2003-06-18
MX9703683A (es) 1997-08-30

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