WO2011016958A2 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
WO2011016958A2
WO2011016958A2 PCT/US2010/041948 US2010041948W WO2011016958A2 WO 2011016958 A2 WO2011016958 A2 WO 2011016958A2 US 2010041948 W US2010041948 W US 2010041948W WO 2011016958 A2 WO2011016958 A2 WO 2011016958A2
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WIPO (PCT)
Prior art keywords
alkyl
counterion
salt
anionic surfactant
integer
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PCT/US2010/041948
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English (en)
French (fr)
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WO2011016958A4 (en
WO2011016958A3 (en
Inventor
Ming Tang
Hiroshi Oh
Sen Liu
Victor Manuel Arredondo
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The Procter & Gamble Company
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Priority to CN2010800337212A priority Critical patent/CN102471733A/zh
Priority to US12/895,963 priority patent/US20110021402A1/en
Publication of WO2011016958A2 publication Critical patent/WO2011016958A2/en
Publication of WO2011016958A3 publication Critical patent/WO2011016958A3/en
Publication of WO2011016958A4 publication Critical patent/WO2011016958A4/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds

Definitions

  • the present invention relates to solid detergent composition
  • solid detergent composition comprising the salt of an anionic surfactant and of alkylamine counterion, in particular a monopropanolamine counterion.
  • Solid detergent compositions typically comprise anionic detergent surfactants.
  • Surfactants perform many functions in a detergent composition such as the cleaning function and the sudsing function of the compositon.
  • salts are compounds composed of cations (positively charged ions) and anions (negative ions) so that the product is electrically neutral (without a net charge).
  • Salts that produce hydroxide ions when dissolved in water are basic salts and salts that produce hydronium ions in water are acid salts.
  • Neutral salts are those that are neither acid nor basic salts.
  • Zwitterions contain an anionic centre and a cationic centre in the same molecule but are not considered to be salts. Examples include amino acids, many metabolites, peptides and proteins. When salts are dissolved in water, they are called electrolytes.
  • anionic surfactants When the anionic surfactants are manufactured, they are often acidic. The acids are commonly neutralized with caustic (NaOH). The acid and caustic form a surfactant sodium salt. The sodium cations from the caustic are often referred to as "counterions" to the surfactant anions. In order to solubilise and stabilize these surfactants for shipping and future processing, water and other solvents are often added.
  • the solution contains the anionic surfactant salt or electrolyte that includes the counterion.
  • the solution containing surfactant and possibly a solvent that does not contain additional ingredients of a detergent may be referred to as a "paste".
  • the inventors have found that anionic surfactants neutralized with sodium counterion could still be improved in terms of sudsing benefit.
  • the sudsing benefit should be improved without substantially affecting the rinsing profile and/or the cleaning CM3418/SK
  • detergent compositions in particular detergent composition comprising a low level of builder(s) and/or surfactant(s), comprising the salt of an anionic surfactant and an alkylamine counterion, in particular the salt of an anionic surfactant and a monopropanolamine counterion.
  • the present invention concerns a solid detergent composition
  • a solid detergent composition comprising the salt of an anionic surfactant and of an alkylamine counterion, the detergent composition comprising less than 10% of phosphate and aluminosilicate builder(s) and/or the detergent composition comprising less than 15% of surfactant(s) and/or the salt of an anionic surfactant and of an alkylamine counterion comprising the salt of an anionic surfactant and of a monopropanolamine counterion.
  • the invention concerns a solid detergent composition
  • a solid detergent composition comprising the salt of an anionic surfactant and of a monopropanolamine counterion.
  • the invention concerns a solid detergent composition
  • a solid detergent composition comprising less than 10% of phosphate and aluminosilicate builder(s) and comprising the salt of an anionic surfactant and of an alkylamine counterion.
  • the invention concerns a solid detergent composition
  • a solid detergent composition comprising less than 15% of surfactant(s) and comprising the salt of an anionic surfactant and of an alkylamine counterion.
  • the composition is in granulated form or in the form of tablet.
  • the solid detergent composition of the invention comprises at least one salt of an anionic surfactant and of an alkylamine counterion, in particular of a monopropanolamine counterion.
  • the detergent composition may comprise at least 0.1%, or 0.2% or 0.3%, in particular from 0.4% to 90%, typically from 0.45% to 10%, or from 0.5% to 5% by weight of salts of an anionic surfactant and of an alkylamine counterion.
  • the detergent composition may comprise at least 0.1%, or 0.2%, or 0.3%, in particular from 0.4% to 90%, typically from 0.45% to 10%, or from 0.5% to 5% by weight of salts of an anionic surfactant and of a monopropanolamine counterion.
  • the ratio of salt(s) of an anionic surfactant and of an alkylamine counterion to the total amount of salt(s) of an anionic surfactant may be between 0.01 and 1, in particular may be between 0.02 and 0.9, and is typically between 0.03 and 0.3, or between 0.05 and 0.2, or even between 0.07 and 0.13.
  • the ratio of salt(s) of anionic surfactant and of monopropanolamine counterion to the total amount of salt(s) of anionic surfactant may be between 0.01 and 1, in particular may be between 0.02 and 0.9, and is typically between 0.03 and 0.3, or between 0.05 and 0.2, or even between 0.07 and 0.13.
  • the salt of an anionic surfactant and of an alkylamine counterion comprises any anionic surfactant and any alkylamine counterion, preferably any monopropanolamine counterion, which can form a salt together.
  • the alkylamine counterion and the anionic surfactant may be selected from the one disclosed below.
  • alkylamine counterion refers to a counterion comprising at least one carbon atom and an amine. When they are neutralizing the anionic surfactant, the alkylamine forms the cationic, conjugate acid of the molecule. This cation may properly be referred to as a "alkylammonium" counterion, however, for the sake of consistency, the term "alkylamine” or
  • alkylamine counterion will be used for purposes of this disclosure.
  • the alkylamine counterion comprises at least 2 or even at least 3 carbon atoms.
  • the alkylamine counterion may comprise 4 or 5 or more carbon atoms but will usually comprise 3 carbon atoms.
  • the alkylamine counterion preferably comprises a substitution of hydroxyl.
  • Example of alkylamine counterion includes monoethanolamine (MEA), choline and propanolamine counterions.
  • the alkylamine counterion is a propanolamine counterion.
  • the term “propanolamine” refers to “monopropanolamines” only. When they are neutralizing the anionic surfactant, the propanolamine forms the cationic, conjugate acid of the molecule. This cation may properly be referred to as a "propanolammonium" counterion, however, for the sake of consistency, the term “propanolamine” or “propanolamine counterion" will be used for purposes of this disclosure.
  • "propanolamine counterion” or the use of the term
  • propanolamine in the context of an ion, refers to the cationic, conjugate acid of the propanolamine.
  • Preferred propanolamines suitable for use as counterions in embodiments of the present disclosure include 2-amino-l-propanol (“2AP”), monoisopropanolamine (“MIPA” or "1- amino-2-propanol”), and l-amino-3-propanol.
  • the propanolamines is selected from 2AP, MIPA, and combinations thereof.
  • the propanolamine is 2AP.
  • 2AP can be made from glycerin, which is a feedstock made from naturally renewable resources.
  • Other counterions, such as MEA, and MIPA are derived from petroleum, which is non-renewable. Further, because it is derived from oil, the price of MEA and MIPA are dependent on the price of oil, while 2AP is not.
  • 2AP may exist in two enantiomeric forms.
  • the conversion of glycerin to 2AP may provide a racemic mixture of the R and S isomers or may also provide it as a single enantiomer by selecting the appropriate chiral catalyst-ligand technology.
  • the anionic surfactant which is part of the slat of an anionic surfactant and of an alkylamine counterion may comprise any anionic surfactant which can be neutralized by a propanolamine counterion.
  • the anionic surfactant may comprise anionic surfactants selected from alkyl ester sulfonate(s); linear, branched, and modified alkylbenzene sulfonate(s); CiO-Ci 8 alkyl alkoxy sulfates; Cio- 2 0 primary, branched-chain and random alkyl sulfates; CiO-Ci 8 secondary (2,3) alkyl sulfates; Ci O -Ci 8 alkyl alkoxy carboxylate(s); fatty acid(s); mid-chain branched alkyl sulfate(s); mid-chain branched alkyl alkoxy sulfate(s); alpha-olefin sulfonate(s); phosphate
  • MES alkyl ester sulfonate surfactants, commonly used in methyl ester sulfonate form.
  • MES surfactants useful herein include sulfonated fatty acid alkyl esters of the formula R-CH(SO3 " )-COOR', wherein R is, on the average, a C 6 to C 22 alkyl and R' is on the average a Ci to Cg alkyl.
  • the hydrophobic portion of these sulfonated alkyl esters have the sulfonate group at the ⁇ -position, i.e., the sulfonate group is positioned at the carbon atom adjacent to the carbonyl group.
  • the alkyl portion of the hydrophobic portion which corresponds to the R portion of the sulfonated fatty acid alkyl esters, is on the average a C 6 to C 22 alkyl.
  • the alkyl portion of this hydrophobic portion, R has a straight-chain of an average length C$ to C 16 hydrocarbon particularly when R' is methyl.
  • R' forming the ester portion of the sulfonated alkyl esters, is on the average a Ci to Cs alkyl.
  • R' is on the average a Ci to C 6 alkyl, and most preferably a Ci alkyl, i.e., methyl.
  • the distribution is such that R is, on the average, a Ci 4 to C 16 alkyl
  • the distribution is such that R is, on the average, a Ci 2 to C 16 alkyl (approximately, for example, a 3% Ci 2 , 28% Ci 4 , 69% C 1 6 mixture) and R' is methyl.
  • the distribution is such that R is, on the average, a do to C 16 alkyl (approximately, for example, a 60% C 1 0, 35% Ci 2 , 5% Ci 4 mixture) and R' is methyl.
  • the distribution is such that R is, on the average, a Ci 2 to Ci 4 alkyl (approximately, for example, a 65% Ci 2 , 30% Ci 4 mixture).
  • a Ci 2 to Ci 4 alkyl approximately, for example, a 65% Ci 2 , 30% Ci 4 mixture.
  • R and R' may also be employed.
  • the methyl ester sulfonate has an average carbon length of about 16.
  • R' could be ethyl (C 2 ), n- propyl & i-propyl (C 3 ), n-butyl, i-butyl (C 4 ), n-pentyl (C 5 ) and n-hexyl (C 6 ).
  • alkyl ester surfactants neutralized with an alkali metal or an alkaline earth metal have been well described and are known to those skilled in art the art. See, for example, U.S. Patent Nos.: 4,671,900; 4,816,188; 5,329,030; 5,382,677; 5,384,422; 5,475,134; 5,587,500; 6,780,830. MES as such is commercially available from Huish.
  • anionic surfactants useful herein include any of the conventional anionic surfactant types typically used in detergent products. These include alkyl benzene sulfonates as well as alkoxylated or non-alkoxylated alkyl sulfates.
  • Exemplary anionic surfactants are Cio-i ⁇ alkyl benzene sulfonates, preferably Cn -I4 alkyl benzene sulfonates.
  • the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS".
  • Alkyl benzene sulfonates, and particularly LAS, are well known in the art.
  • Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383.
  • Preferred are the linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
  • Cn- Ci 4 e.g., Ci 2
  • LAS is a specific example of such surfactants.
  • exemplary akylbenzene sulfonates include modified alkylbenzene sulfonate
  • MLAS may comprise a mixture, preferably consisting essentially of : (a) from about 15% to about 99%, preferably from about 15% to about 60%, more preferably from about 20% to about 40%, by weight of a mixture of branched alkylbenzene sulfonates having formula:
  • L is an acyclic aliphatic moiety consisting of carbon and hydrogen, the L having two methyl termini and the L having no substituents other than A, R 1 and R 2 ; and wherein the mixture of branched alkylbenzene sulfonates contains two or more, preferably at least three, optionally more, of the branched alkylbenzene sulfonates differing in molecular weight of the anion of the formula (I), and wherein the mixture of branched alkylbenzene sulfonates has a sum of carbon atoms in R 1 , L and R 2 of from 9 to 15, preferably from 10 to 14; an average aliphatic carbon CM3418/SK
  • R 1 is C 1 -C 3 alkyl, preferably Ci-C 2 alkyl, more preferably methyl
  • R 2 is selected from H and C 1 -C 3 alkyl, preferably H and C 1 -C 2 alkyl, more preferably H and methyl, more preferably H and methyl provided that in at least about 0.5, more preferably 0.7, more preferably 0.9 to 1.0 mole fraction of the branched alkylbenzene sulfonates, R 2 is H;
  • A is a benzene moiety, typically A is the moiety-Cot ⁇ -, with the SO 3 " moiety of Formula (I) in para-position to the L moiety, though in some proportion, usually no more than about 5%, preferably from 0 to 5% by weight, the
  • A is as defined hereinbefore and Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein the Y has a sum of carbon atoms of from 9 to 15, preferably from 10 to 14, and the Y has an average aliphatic carbon content of from about 10.0 to about 14.0, preferably from about 11.0 to about 13.0, more preferably 11.5 to 12.5 carbon atoms; and wherein the modified alkylbenzene sulfonate surfactant mixture is further characterized by a 2/3 -phenyl index of from about 160 to about 275, preferably from about 170 to about 265, more preferably from about 180 to about 255; and also preferably wherein the modified alkylbenzene sulfonate surfactant mixture has a 2-methyl-2- phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0.1, more preferably still, from 0 to 0.05.
  • anionic surfactant includes ethoxylated alkyl sulfate surfactants.
  • ethoxylated alkyl sulfate surfactants include ethoxylated alkyl sulfate surfactants.
  • alkyl ether sulfates or alkyl polyethoxylate sulfates are those which correspond to the formula:
  • R' is a Cg-C 2O alkyl group and n is from about 1 to 20.
  • R' is C 10 -C 18 alkyl and n is from about 0.1 to 15.
  • n is from about 1 to
  • R' is a C 12 -C 16 , n is from about 1 to 6.
  • EOx indicates that the alkoxy group is an ethoxy group
  • x indicates the number of ethoxy groups in each chain.
  • alkyl ether sulfates will generally be used in the form of mixtures comprising varying
  • n R' chain lengths and varying degrees of ethoxylation.
  • Alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present.
  • alkyl sulfates surfactants are those produced by the sulfation of higher C 10 -C 20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula:
  • R is typically a linear C 1 0-C 2 0 alkyl group, which may be straight chain or branched chain.
  • R is a C 10 -C 15 alkyl, more specifically R is Ci 2 -Ci 4 .
  • Another anionic surfactant useful herein includes secondary (2,3) alkyl sulfates having formulae CH 3 -(CH 2 ) X -CH(OS(V)-CH 3 or CH 3 -(CH 2 ) y -CH(OSO 3 >CH 2 -CH 3 .
  • Non-limiting examples of a preferred secondary alkyl sufate include the one where x is at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9.
  • anionic surfactant includes ethoxylated alkyl carboxylate surfactants.
  • ethoxylated alkyl carboxylate surfactants include ethoxylated alkyl carboxylate surfactants.
  • alkyl ether carboxylates or alkyl polyethoxylate carboxylates are those which correspond to the formula:
  • R' is a Cs-C 2O alkyl group and n is an integer from about 1 to 20.
  • R' is Ci O -Ci 8 alkyl and/or n is from about 1 to 15.
  • R' is a Ci 2 -Ci6 and/or n is from about 1 to 6.
  • alkyl ether carboxylates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will CM3418/SK
  • Fatty acids have the general formula:
  • R is typically a C 9 -C 21 alkyl group, which may be straight chain or branched chain.
  • R is a C 9 -C 17 alkyl, and more specifically R is C 11 -C 15 .
  • Exemplary fatty acids are selected from the group consisting of lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, phytanic acid, behenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, cis-eleostearic acid, trans-eleosteric acid, linolenic acid, arachidonic acid and combinations thereof.
  • Preferred fatty acids can be saturated or unsaturated.
  • Unsaturated fatty acids typically having an iodine value from 15 to 25, preferably from 18 to 22 and a cis: trans isomer ratio from 1:1 to 200:1, preferably fro 10:1 to 200:1.
  • Preferred sources of fatty acid are selected from the group consisting of coconut, soybean, tallow, palm, palm kernel, rapeseed, lard, sunflower, corn, safflower, canola, olive, peanut and combinations thereof.
  • Mid-chain Branched Alkyl Sulfates are selected from the group consisting of coconut, soybean, tallow, palm, palm kernel, rapeseed, lard, sunflower, corn, safflower, canola, olive, peanut and combinations thereof.
  • Exemplary anionic surfactants include mid-chain branched alkyl sulfates as discussed in U.S. Patents 6,020,303 and US 6,060,443.
  • Mid-chain branched alkyl sulfates may comprise at least about 0.5%, preferably at least about 5%, more preferably at least about 10%, most preferably at least about 20%, by weight of longer alkyl chain, mid-chain branched surfactant compounds of the formula:
  • a b is a hydrophobic C 9 to C 22 (total carbons in the moiety), preferably from about Ci 2 to about Ci 8 , mid-chain branched alkyl moiety having: (1) a longest linear carbon chain attached to the— X— B moiety in the range of from 8 to 21 carbon atoms; (2) one or more Q -3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the CM3418/SK
  • the surfactant composition has an average total number of carbon atoms in the A b — X moiety in the above formula within the range of greater than 14.5 to about 17.5 (preferably from about 15 to about 17);
  • (b) B is a hydophilic moiety selected from sulfates.
  • X is selected from -CH 2 - and -C(O)-.
  • Preferred mid-chain branched alkyl sulfates herein comprise longer alkyl chain, mid- chain branched surfactant compounds of the above formula wherein the A b moiety is a branched primary alkyl moiety having the formula:
  • R, Rl, and R2 are each independently selected from hydrogen and C 1 -C 3 alkyl (preferably methyl), provided R, R 1 , and R 2 are not all hydrogen and, when z is 0, at least R or R 1 is not hydrogen; w is from 0 to 13; x is from 0 to 13; y is from 0 to 13; z is from 0 to 13; and w+x+y+z is from 7 to 13.
  • mid-chain branched alkyl sulfates comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A b moiety is a branched primary alkyl moiety having the formula selected from:
  • Still other exemplary anionic surfactants include mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Patents 6,008,181 and US 6,020.303
  • Mid-chain branched alkyl alkoxy sulfates comprise from about 0.001% to about 100% of one or more (preferably a mixture of two or more) mid-chain branched primary alkyl alkoxylated sulfates having the formula:
  • the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m.
  • CM3418/SK a distribution with average degree of alkoxylation corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m.
  • the mid-chain branched alkyl alkoxy sulfates comprise a mixture of mid-chain branched primary alkyl alkoxylated sulfate surfactants, said mixture comprising at least about 5% by weight of two or more mid-chain branched primary alkyl alkoxylated sulfates having the formula:
  • the mid-chain branched alkyl alkoxy sulfates may comprise compounds of formula:
  • a is an integer from 2 to 11
  • b is an integer from 1 to 10
  • a+b is 8 or 9
  • EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 0.6 to about 5.
  • olefin sulfonates which are compounds produced by the sulfonation of alpha-olefin by means of uncomplexed sulfur trioxide followed by neutralization of the acid reaction mixture under conditions such that sultones formed in the reaction are hydrolyzed to give corresponding hydroxyalkanesulfonates.
  • the alpha-olefins from which the olefin sulfonates are derived are mono-olefins having from about 8 to about 24 carbon atoms, preferably from about 12 to about 16 carbon atoms. Preferably, they are straight chain olefins.
  • Exemplary alpha-olefin sulfonates for use in the disclosure herein have the general formula:
  • R-CH CH-CH2-SO 3 " (2,3-alkenylsulfonate) or R-CH(OH)-CH2-CH2-SO 3 " (3-hydroxy- alkanesulfonate, where R is a linear or branched alkyl of about 8 to 20 carbon atoms.
  • suitable alpha- olefins include 1 -olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1- eicosene and 1-tetracosene.
  • Phosphate esters are any materials of the general formula:
  • R and R' are C 6 -C 20 alkyl or ethoxylated alkyl groups.
  • R and R' are of the general formula: wherein the alkyl substituent is Cio -C 16 an d Y is between 0 and about 4. Most preferably the alkyl substituant of that formula is Cio -C 16 and Y is between about 2 and about 4.
  • Such compounds may be prepared by known methods from phosphorus pentoxide, phosphoric acid, or phosphorus oxy halide and alcohols or ethoxylated alcohols.
  • Salt of an anionic surfactant and of a monopropanolamine counterion may comprised salts selected from salts of formula R-CH(CH 3 )-A-SO 3 ⁇ :+NH 3 CH 2 (CH 3 )CH 2 OH with A being a benzene ring and R being a Ci 0 -Ci 6 alkyl, R-CH 2 (SO 3 )COOCH 3 " :+NH 3 CH 2 (CH 3 )CH 2 OH with R being a C 6 -C 22 alkyl, ROSO 3 ⁇ NH 3 CH 2 (CH 3 )CH 2 OH, with R being a Ci 0 -C 20 alkyl, RO(CH 2 CH 2 O) X OSO 3 ⁇ NH 3 CH 2 (CH 3 )CH 2 OH with R being a
  • Such salts includes in particular:
  • a surfactant paste comprising a salt of the invention may be prepared by adding a alkylamine counterion to an acid surfactant to neutralize the acid surfactant.
  • particles comprising the salt of an anionic surfactant and of alkylamine counterion may be prepared by agglomeration or spray drying.
  • the particles comprising the salt of an anionic surfactant and of alkylamine counterion are dry-added to the solid detergent composition.
  • the solid detergent composition may be a laundry detergent composition or a dish washing detergent composition.
  • the laundry detergent composition is formulated for use in an automatic washing machine or for hand-washing use.
  • the solid detergent composition may be in the form of an agglomerate, granule, flake, extrudate, bar, tablet or any combination thereof.
  • the solid composition can be made by methods such as dry-mixing, agglomerating, compaction, spray drying, pan-granulation, spheronization or any combination thereof.
  • the solid composition typically has a bulk density of from 300 g/1 to
  • 1,500 g/1 typically from 500 g/1 to 1,000 g/1.
  • the solid detergent composition may comprise one or more adjunct ingredient(s).
  • adjunct ingredient(s) the precise nature of these additional adjunct components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used.
  • Suitable adjunct materials include, but are not limited to, builder, additional surfactants, CM3418/SK
  • the detergent composition may comprise one or more additional surfactant(s).
  • the additional surfactant(s) may be selected from nonionic surfactants, additional salts of anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof.
  • the additional salt(s) of anionic surfactant(s) may be in the form of a salt of an anionic surfactant (as defined above, for example: alkyl ester sulfonate(s); linear, branched, and modified alkylbenzene sulfonate(s); CiO-Ci 8 alkyl alkoxy sulfates; Cio- 2 0 primary, branched-chain and random alkyl sulfates; Ci O -Ci 8 secondary (2,3) alkyl sulfates; Ci O -Ci 8 alkyl alkoxy carboxylate(s); fatty acid(s); mid-chain branched alkyl sulfate(s); mid-chain branched alkyl alkoxy sulfate(s); alpha-olefin sulfonate(s); phosphate ester(s)) with a counterion other than an alkylamine counterion.
  • the counterion may be a proto
  • compositions of the invention may comprise non-ionic surfactant.
  • non-ionic detersive surfactant(s) is generally present in amounts of from 0.5 to 20wt%, or from 2wt% to 4wt%.
  • the composition may comprise a cationic detersive surfactant.
  • a cationic detersive surfactant typically the composition comprises from 0.1 wt% to 10 wt%, or from lwt% to 2wt% cationic detersive surfactant.
  • Suitable cationic detersive surfactants are alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, and alkyl ternary sulphonium compounds.
  • the cationic detersive surfactant can be selected from the group consisting of: alkoxylate quaternary ammonium (AQA) surfactants as described in more detail in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium surfactants as described in more detail in US 6,004,922; polyamine cationic surfactants as described in more detail in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as described in more detail in US 4,228,042, US 4,239,660, US 4,260,529 and US 6,022,844; amino surfactants as described in more detail in US 6,221,825
  • Highly preferred cationic detersive surfactants are mono-Cg-io alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-Cio- 12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
  • Cationic surfactants such as Praepagen HY (tradename Clariant) may be useful and may also be useful as a suds booster.
  • the detergent composition may comprise one or more builders.
  • the subject composition will typically comprise from 1% to about 40%, typically from 2 to 25%, or even from about 5% to about 20%, or from 8 to 15% by weight of builder.
  • Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, layered silicates, such as SKS-6 of Clariant ® , alkaline earth and alkali metal carbonates, aluminosilicate builders, such as zeolite, and polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, fatty acids, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, CM3418/SK
  • oxydisuccinic acid polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • the detergent compositions of the present invention may comprise from 0 to 20%, in particular less than 15% or 10%, for example less than 5% of zeolite.
  • the detergent composition comprises from 0 to 20%, in particular less than 15% or 10%, for example less than 5% of aluminosilicate builder(s).
  • the detergent composition of the present invention may comprise from 0 to 20%, in particular less than 15% or 10%, for example less than 5% of phosphate builder(s).
  • the solid detergent composition may comprise from 0 to 20%, in particular less than 15% or 10%, for example less than 5% of phosphate builder(s) and of aluminosilicate builder(s).
  • the total amount of phosphate builder(s), aluminosilicate builder(s), polycarboxylic acid builder(s), and additional silicate builder(s) in the detergent composition may be comprised from 0 to 25%, or even from 1 to 20%, in particular from 1 to 15%, especially from 2 to 10%, for example from 3 to 5%, by weight.
  • the detergent compositions of the present invention may comprise from 0 to 35%, in particular less than 25% or 20% or 15% or 10%, for example less than 5% of sodium carbonate.
  • the composition may further comprise any other supplemental builder(s), chelant(s), or, in general, any material which will remove calcium ions from solution by, for example, sequestration, complexation, precipitation or ion exchange.
  • the composition may comprise materials having at a temperature of 25 0 C and at a 0. IM ionic strength a calcium binding capacity of at least 50 mg/g and a calcium binding constant log K Ca 2+ of at least 3.50.
  • the total amount of phosphate builder(s), aluminosilicate builder(s), polycarboxylic acid builder(s), additional silicate builder(s), and other material(s) having a calcium binding capacity superior to 50mg/g and a calcium binding constant higher than 3.50 in the composition may be comprised from 0 to 25%, or even from 1 to 20%, in particular from 1 to 15%, especially from 2 to 10%, for example from 3 to 5%, by weight.
  • the composition may further comprise a flocculating aid.
  • the composition comprises at least 0.3% by weight of the composition of a flocculating aid.
  • the composition may also be substantially free of flocculating aid.
  • the flocculating aid is polymeric.
  • the flocculating aid is a polymer comprising monomer units selected from the group consisting of ethylene oxide, acrylamide, acrylic acid and mixtures thereof.
  • the flocculating aid is a polyethyleneoxide.
  • aid has a molecular weight of at least 100,000 Da, in particular from 150,000 Da to 5,000,000 Da or even from 200,000 Da to 700,000 Da.
  • compositions of the present invention may comprise one or more bleaching agents.
  • a bleaching agent when used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about
  • bleaching agents include bleaching catalysts, photobleaches for example Vitamin K3 and zinc or aluminium phtalocyanine sulfonate; bleach activators such as tetraacetyl ethylene diamine
  • TAED nonanoyloxybenzene sulphonate
  • HBS hydrogen peroxide
  • sources of hydrogen peroxide such as inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof, optionally coated, suitable coatings including inorganic salts such as alkali metal; and mixtures thereof.
  • the amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1
  • the composition may contain components that may tint articles being cleaned, such as fluorescent whitening agent.
  • fluorescent whitening agent any fluorescent whitening agent suitable for use in a detergent composition may be used in the composition of the present invention.
  • the most commonly used fluorescent whitening agents are those belonging to the classes of diaminostilbene-sulphonic acid derivatives, diarylpyrazoline derivatives and bisphenyl-distyryl derivatives.
  • Tinopal ® DMS is the disodium salt of 4,4'-bis-(2-morpholino-4 anilino- s-triazin-6-ylamino) stilbene disulphonate.
  • Tinopal CBS is the disodium salt of 2,2'-bis-(phenyl- styryl) disulphonate.
  • FABRIC HUEING AGENTS- Fluorescent whitening agents emit at least some visible light.
  • fabric hueing agents alter the tint of a surface as they absorb at least a portion of the visible light spectrum.
  • Suitable fabric hueing agents include dyes and dye-clay conjugates, and may also include pigments.
  • Suitable dyes include small molecule dyes and polymeric dyes.
  • Suitable small molecule dyes include small molecule dyes selected from the group consisting of CM3418/SK
  • compositions of the present invention can contain polymeric dispersing agents. These polymeric dispersing agents, if included, are typically at levels up to about 5%, typically from about 0.2% to about 2.5%, more typically from about 0.5% to about 1.5%.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates, substituted (including quarternized and oxidized) polyamine polymers, and polyethylene glycols, such as: acrylic acid-based polymers having an average molecular of about 2,000 to about 10,000; acrylic/maleic-based copolymers having an average molecular weight of about 2,000 to about 100,000 and a ratio of acrylate to maleate segments of from about 30:1 to about 1:1; maleic/acry lie/vinyl alcohol terpolymers; polyethylene glycol (PEG) having a molecular weight of about 500 to about 100,000, typically from about 1,000 to about 50,000, more typically from about 1,500 to about 10,000; and water soluble or dispersible alkoxylated polyalkyleneamine materials.
  • polymeric polycarboxylates such as: acrylic acid-based polymers having an average molecular of about 2,000 to about 10,000; acrylic/maleic-based copolymers having an average molecular weight of about 2,000 to about 100,000 and a ratio of acryl
  • compositions of the present invention can also contain polymeric soil release agent, polymeric soil release agent, or "SRA", have 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, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters; sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone; nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters; an oligomer having empirical formula (CAP) 2 (EG/PG) 5 (T) 5 (SIP)i which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l,2-propylene (EG/PG) units and which is typically terminated with end-caps (CAP), typically modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l
  • CAP, EG/PG, PEG, T and SIP are as defined hereinabove
  • DEG represents di(oxyethylene)oxy units
  • SEG represents units derived from the sulfoethyl ether of glycerin and related moiety units
  • B represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone
  • a is from about 1 to about 12
  • b is from about 0.5 to about 25
  • c is from 0 to about 12
  • d is from 0 to about 10
  • e is from about 1.5 to about
  • f is from 0 to about 12
  • g is from about 0.05 to about 12
  • h is from about 0.01 to about 10 and a, b
  • the composition of the invention may further comprise an enzyme.
  • the enzymes When present in the detergent composition, the enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5% or 0.02% enzyme protein by weight of the composition.
  • Suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • CM3418/SK hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannana
  • ENZYME STABILIZERS - Enzymes for use in detergents can be stabilized by various techniques.
  • the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes.
  • a reversible protease inhibitor such as a boron compound, can be added to further improve stability.
  • compositions of the invention may comprise catalytic metal complexes.
  • one type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic
  • compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. 5,597,936; U.S. 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. 5,597,936, and U.S. 5,595,967.
  • compositions herein may also suitably include a transition metal complex of ligands such as bispidones (WO 05/042532 Al) and/or macropolycyclic rigid ligands - abbreviated as "MRLs".
  • ligands such as bispidones (WO 05/042532 Al) and/or macropolycyclic rigid ligands - abbreviated as "MRLs”.
  • MRLs macropolycyclic rigid ligands
  • Suitable transition-metals in the instant transition-metal bleach catalyst include, for example, manganese, iron and chromium.
  • Suitable MRLs include 5,12-diethyl-l,5,8,12- tetraazabicyclo[6.6.2]hexadecane.
  • Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. 6,225,464. CM3418/SK
  • compositions of the invention may comprise a softening agent such as clay for softening through the wash.
  • the composition may additionally comprise a charged polymeric fabric- softening boosting component.
  • compositions of the invention may comprise a colorant, typically a dye or a pigment.
  • a colorant typically a dye or a pigment.
  • preferred dyes are those which are destroyed by oxidation during a laundry wash cycle. To ensure that the dye does not decompose during storage it is preferable for the dye to be stable at temperatures up to 40°C. The stability of the dye in the composition can be increased by ensuring that the water content of the composition is as low as possible. If possible, the dyes or pigments should not bind to or react with textile fibres. If the colorant does react with textile fibres, the colour imparted to the textiles should be destroyed by reaction with the oxidants present in laundry wash liquor. This is to avoid coloration of the textiles, especially over several washes.
  • preferred dyes include but are not limited to Basacid® Green

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