EP1196525B1 - Polyamine und mittelseitenkettige tenside enthaltende wäschewaschmittelzusammensetzungen - Google Patents

Polyamine und mittelseitenkettige tenside enthaltende wäschewaschmittelzusammensetzungen Download PDF

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Publication number
EP1196525B1
EP1196525B1 EP00947338A EP00947338A EP1196525B1 EP 1196525 B1 EP1196525 B1 EP 1196525B1 EP 00947338 A EP00947338 A EP 00947338A EP 00947338 A EP00947338 A EP 00947338A EP 1196525 B1 EP1196525 B1 EP 1196525B1
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weight
units
mixtures
surfactant
acid
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French (fr)
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EP1196525A1 (de
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Kenneth Nathan Price
Eugene Paul Gosselink
Randall Scott Deinhammer
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to laundry detergent compositions which provide enhanced hydrophilic soil, inter alia , clay, removal benefits.
  • the laundry detergent compositions of the present invention combine polyamines and a surfactant system which comprises mid-chain branched surfactants inter alia mid-chain branched alkyl sulfates.
  • the laundry detergent compositions of the present invention may take any form, inter alia, solid, including granular, powder, tablet, bar, or liquid, including gels, paste, thixotropic liquids.
  • the present invention further relates to methods for cleaning fabric having heavy clay soil deposits.
  • Fabric especially clothing, can become soiled with a variety of foreign substances ranging from hydrophobic stains (grease, oil) to hydrophilic stains (clay).
  • the level of cleaning which is necessary to remove said foreign substances depends to a large degree upon the amount of stain present and the degree to which the foreign substance has contacted the fabric fibers.
  • Grass stains usually involve direct abrasive contact with vegetative matter thereby producing highly penetrating stains.
  • Clay soil stains although in some instances contacting the fabric fibers with less force, nevertheless provide a different type of soil removal problem due to the high degree of charge associated with the clay itself. This high surface charge density may act to repel some laundry adjunct ingredients, inter alia, clay dispersants, thereby resisting any appreciable peptization and dispersal of the clay into the laundry liquor.
  • a surfactant per se is not all that is necessary to remove unwanted clay soils and stains. In fact, most surfactants by themselves in water are surprisingly poor at removing clay soils from fabric. not all surfactants work equally well on all types of stains.
  • polyamine-based hydrophilic soil dispersants are added to laundry detergent compositions to "carry away" clay soils from the fabric surface and to stabilize the removed particles in solution sufficiently to minimize the possibility that the clay soil will be re-deposited upon the fabric.
  • the clay can be initially removed from the soiled fabric, especially in the case of hydrophilic fibers, inter alia, cotton, there will be nothing in solution for the dispersants to bind to and keep suspended.
  • polyamine-based agents also referred to herein as "polyamines”
  • a surfactant system comprising one or more mid-chain branched surfactants provides enhanced removal of clay and other hydrophilic soils from fabric.
  • the first aspect of the present invention relates to a laundry detergent composition
  • a laundry detergent composition comprising:
  • the present invention also relates to hydrophilic soil cleaning systems which comprise polyamines which can be tailored to the specific surfactant system or laundry detergent form, i.e., liquid, granular.
  • the present invention further relates to laundry detergent compositions which are effective in removing clay-like soils under circumstances of high soil loading or high water hardness.
  • the present invention also relates to a method for removing hydrophilic stains from fabric by contacting fabric in need of cleaning with a composition according to the present invention.
  • the present invention relates to the surprising discovery that the combination of a polyamine and a surfactant system which comprises at least one mid-chain branched surfactant provides enhanced benefits for removal of clay soil from fabric especially clothing. It has been surprisingly discovered that the formulator, by selecting the molecular weight of the parent backbone, relative degree of quaternization, relative amount of N-oxide formation of the polyamine backbone, the type and relative degree of units which substitute the polyamine backbone, inter alia, cationic, anionic, and the nature of the amine backbone itself, inter alia, polyhexyleneimine, the formulator is able to form a polymer which can be tailored for optimization depending upon the desired execution. For example, the formulator may opt to use one type of polymer for a liquid embodiment targeted for use in a high soil loading context and another polymer for use in a granular detergent used for washing fabric in cold water.
  • the polyamines of the present invention interact with the mid-chain branched surfactants in a manner which makes the adsorption in the clay more efficacious by changing the anionic nature of the surface. It is believed this system is more effective in peptizing or breaking up the clay aggregates on the surface, thus allowing the inherent agitation associated with the laundry process (for example, the agitation provided by an automatic washing machine) act to break the surface-modified particles loose from the fabric surface and disperse them into solution.
  • the clay and other hydrophilic particles which are removed by the compositions of the present invention are those types of stains or particles which are not well removed by normal surfactant/dispersant systems.
  • nonionic surfactants are highly desirable components of the herein described granular laundry detergent compositions, their absence or presence does not affect the ability of the polyamine/mid-chain branched surfactant system to enhance clay soil removal.
  • the laundry detergent compositions of the present invention may take any form, for example, solid, including granular, powder, tablet, or liquid, including gels, paste, thixotropic liquids, etc.
  • the polyamines of the present invention comprise from 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 2% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of the compositions of the present invention.
  • compositions which may take any form, for example, solids (i.e., powders, granules, extrudates, tablets), gels, thixotropic liquids, and pourable liquids (i.e., dispersions, isotropic solutions).
  • the polymers of the present invention are comprised of a polyamine backbone wherein the backbone units which connect the amino units can be modified by the formulator to achieve varying levels of product enhancement, inter alia, boosting of clay soil removal by surfactants, greater effectiveness in high soil loading usage.
  • the formulator may preferably substitute one or more of the backbone amino unit hydrogens by other units, inter alia, alkyleneoxy units having a terminal anionic moiety.
  • the nitrogens of the backbone may be oxidized to the N-oxide. Preferably at least two of the nitrogens of the polyamine backbones are quaternized.
  • cationic units are defined as “units which are capable of having a positive charge”.
  • the cationic units are the quaternary ammonium nitrogens of the polyamine backbones or quaternary ammonium units which comprise the units which substitute the polyamine backbone.
  • anionic units are defined as "units which are capable of having a negative charge”.
  • the anionic units are "units which alone, or as a part of another unit, substitute for hydrogens along the polyamine backbone" a non-limiting example of which is a -(CH 2 CH 2 O) 20 SO 3 Na which is capable of replacing a backbone hydrogen on a nitrogen or oxygen atom.
  • Preferred polymers of the present invention have the formula: wherein R units have the formula -(R 2 O) w R 3 - wherein R 2 and R 3 are each independently selected from the group consisting of C 2 -C 8 linear alkylene, C 3 -C 8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; R 2 units are each ethylene; Y is hydrogen, -SO 3 M, and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, the index w is from 1, to 10. And Q is aquaternising unit selected from the group consisting of C 1 to C 4 linear alkyl, benzyl, and mixtures thereof.
  • R unit having the formula -(R 2 O) w R 3 - is the backbone: -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 - wherein R 2 is propylene and butylene, R 3 is propylene, w is equal to 2.
  • Non-limiting examples of backbones according to the present invention include 1,9-diamino-3,7-dioxanonane; 1,10-diamino-3,8-dioxadecane; 1,12-diamino-3,10-dioxadodecane; 1,14-diamino-3,12-dioxatetradecane.
  • backbones which comprise more than two nitrogens may comprise one or more repeating.units having the formula: H 2 N-[R-NH]- for example a unit having the formula: H 2 N-[CH 2 CH 2 OCH 2 CH 2 NH]- is described herein as 1,5-diamino-3-oxapentane.
  • a backbone which comprises two 1,5-diamino-3-oxapentane units has the formula: H 2 NCH 2 CH 2 OCH 2 CH 2 NHCH 2 CH 2 OCH 2 CH 2 NH 2 .
  • Further suitable repeating units include 1,8-diamino-3,6-diaxaoctane; 1,11-diamino-3,6,9-trioxaundecane; 1,5-diamino-1,4-dimethyl-3-oxaheptane; 1,8-diamino-1,4,7-trimethyl-3,6-dioxaoctane; 1,9-diamino-5-oxanonane; 1,14-diamino-5,10-dioxatetradecane.
  • the present invention affords the formulator with the ability to optimize the polymer for a particular use or embodiment.
  • the backbone quaternization positive charge carriers
  • the anionic capping units of the R 1 units ameliorate the ability of surfactant molecules to interact, and therefore occupy, the cationic sites of the polymers.
  • the amount of anionic moieties needed vary from embodiment to embodiment.
  • Heavy Duty Granular (HDG) compositions which comprise a high amount of linear alkylbenzene sulfonate (LAS) surfactant require a greater number of anionic units per se to be present in the polymers.
  • HDG Heavy Duty Granular
  • the polymers of the present invention provide a greater degree of clay removal when used with the same amount of a non-mid chain branched surfactant.
  • the polymer will have a net negative charge.
  • three quaternized backbone nitrogens will be present for every 5 -SO 3 M capping units.
  • liquid embodiments (HDL) of the present invention are more effective in removing hydrophilic soils when the backbones comprise R units having a greater degree of alkylene unit character and which comprise a lower number of anionic units which cap the R 1 units than the backbones in their HDG counterpart embodiments.
  • polymers of the present invention preferably comprise polyamine backbone which are derivatives of two types of backbone units:
  • the formulator may assemble higher oligomers from these constituent parts by using R units of types (iii), (iv), and (v).
  • R units of types (iii), (iv), and (v) include the epihalohydrin condensate having the formula: or the hybrid oligomer having the formula: wherein each backbone comprises a mixture of R units.
  • the formulator may form polymers which have an excess of charge or an equivalent amount of charge type.
  • An example of a preferred polyamine according to the present invention which has an excess of anionic charged units has the formula: wherein R is a 1,3-propyleneoxy-1,4-butyleneoxy-1,3-propylene unit, w is 2; R 1 is -(R 2 O) t Y, wherein R 2 is ethylene, each Y is -SO 3 - , Q is methyl, m is 0, n is 0, t is 20.
  • R 1 unit it will be recognized by the formulator that not every R 1 unit will have a SO 3 - moiety capping said R 1 unit.
  • the final polyamine mixture comprises at least about 90% Y units which are -SO 3 - units.
  • polyamines which may be present as a formulated admixture or a product by process composition, or a mixture of both. These prefered compounds can be represented by the formulae:
  • the modified polyamine compounds of the present invention comprise a Polyamine Backbone, PA unit, which can be optionally, but preferably grafted.
  • PA unit which can be optionally, but preferably grafted.
  • a preferred PA unit according to the present invention are polyalkyleneimines and polyalkyleneamines having the general formula: wherein R is C 2 -C 12 linear alkylene, C 3 -C 12 branched alkylene, and mixtures thereof; B representing a continuation of the chain structure by branching.
  • the indices w, x, and y have various values depending upon such factors as molecular weight and relative degree of branching.
  • the polyalkyleneimines and polyalkyleneamines which comprise PA units of the present invention are divided into three categories based upon relative molecular weight.
  • the terms polyalkyleneimine and polyalkyleneamine are used interchangeably throughout the present specification and are taken to mean polyamines having the general formula indicated above regardless of method of preparation.
  • R is C 2 -C 12 linear alkylene, C 3 -C 12 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and 1,6-hexylene, more preferred is ethylene.
  • the index w typically has the value of y + 1.
  • the simplest of the low molecular weight polyamines of this type is ethylene diamine which may be present up to about 10% by weight of the PA unit mixture.
  • Non-limiting examples of low molecular weight polyalkyleneimine PA units include diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, tripropylene tetramine, and dihexamethylene triamine.
  • PA units may be used as crude products or mixtures, and if desired by the formulator, these PA units may be used in the presence of small amounts of diamines as described herein above, wherein the amount of diamines, inter alia, ethylene diamine, hexamethylene diamine may be present up to about 10% by weight, of the PA unit mixture.
  • R is C 2 -C 4 linear alkylene, C 3 -C 4 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and mixtures thereof, more preferred is ethylene wherein said polyamines are polyethyleneimines (PEI's).
  • PEI's polyethyleneimines
  • the indices w, x, and y are such that the molecular weight of said polyamines is from about 600 daltons to about 50,000 daltons.
  • the indices w, x, and y will indicate not only the molecular weight of the polyalkyleneimines but also the degree of branching present in the PA unit backbone.
  • R is C 2 -C 3 linear alkylene, preferably R is ethylene.
  • the indices w, x, and y are such that the molecular weight of said polyamines is from about 50,000 daltons to about 1,000,000 (1 million) daltons.
  • the indices w, x, and y will indicate not only the molecular weight of the polyalkyleneimines but also the degree of branching present in the PA unit backbone.
  • a preferred PA unit according to the present invention are the polyvinyl amine homo-polymers or co-polymers having the formula: wherein V is a co-monomer, non-limiting examples of which include vinyl amides, vinyl pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures thereof, all of which can be taken together or in combination with polyvinyl amine to form suitable co-polymerization products suitable for use in the fabric enhancement systems of the present invention.
  • V is a co-monomer, non-limiting examples of which include vinyl amides, vinyl pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures thereof, all of which can be taken together or in combination with polyvinyl amine to form suitable co-polymerization products suitable for use in the fabric enhancement systems of the present invention.
  • the indices m and n are such that the copolymers comprise at least 10%, more preferably at least about 30% of units derived from vinyl amine and wherein further the molecular weight of said copolymers if from about 500 daltons, preferably from about 5,000 daltons to about 50,000 daltons, preferably to about 20,000 daltons.
  • the PA units of the present invention are modified either before or after reaction with a T unit or L unit crosslinking agent.
  • the two preferred types of modifications are grafting and capping.
  • the PA units of the present invention are grafted, that is the PA unit is further reacted with a reagent which elongates said PA unit chain, preferably by reaction of the nitrogens of the PA backbone unit with one or more equivalents of aziridine (ethyleneimine), caprolactam, and mixtures thereof. Grafting units, in contrast to the "capping" units described herein below, can further react on themselves to provide PA unit chain propagation.
  • An example of a preferred grafted PA unit of the present invention has the formula: wherein R, B, w, x, and y are the same as defined herein above and G is hydrogen or an extension of the PA unit backbone by grafting.
  • Non-limiting examples of preferred grafting agents are aziridine (ethyleneimine), caprolactam, and mixtures thereof.
  • a preferred grafting agent is aziridine wherein the backbone is extended by units having the formula: wherein B' is a continuation by branching wherein the graft does not exceed about 12 units, preferably -CH 2 CH 2 NH 2 and the value of the indices p + q have the value from 0, preferably from about 1, more preferably from about 2 to about 7, preferably to about 5.
  • Another preferred grafting unit is caprolactam.
  • the PA units of the present invention can be grafted prior to or after crosslinking with one or more T units described herein below, preferably the grafting is accomplished after crosslinking with said T unit.
  • This allows the formulator to take advantage of the differential reactivity between the primary and secondary amino units of the PA unit backbone thereby allowing the formulator to controllably link said PA units and to also control the amount of subsequent branching which results from the grafting step.
  • PA unit modification is the presence of "capping" units.
  • a PA unit is reacted with an amount of a monocarboxylic acid, non-limiting examples of which are C 1 -C 22 linear or branched alkyl, preferably C 10 -C 18 linear alkyl inter alia lauric acid, myristic acid.
  • the amount of capping unit which is reacted with the PA unit is an amount which is sufficient to achieve the desired properties of the formula.
  • the amount of capping unit used is not sufficient to abate any further crosslinking or grafting which the formulator may choose to perform.
  • T crosslinking units are preferably carbonyl comprising polyamido forming units.
  • the T units are taken together with PA units to form crosslinked modified polyamine compounds having the formula (PA) w (T) x or [(PA) w (T) x ] y [L] z .
  • a preferred embodiment of the present invention includes crosslinked PA units wherein a T unit provides crosslinking between two or more PA units to form a (PA) w (T) x polyamido crosslinked section.
  • a preferred crosslinking T unit has the general formula: wherein R 1 is methylene, phenylene, and mixtures thereof; preferably methylene.
  • the index k has the value from 2 to about 8, preferably to about 4. Preferred values of k are 2, 3, and 4.
  • R 2 is -NH- thereby forming a urethane amide linkage when said R 2 comprising T units react with the backbone nitrogens of the PA units.
  • the value of the index j is independently 0 or 1.
  • R 2 units can result, for example, from the use of diisocyanates as crosslinking agents.
  • dibasic acids which are used as a source for T units in the above formula include succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid, and terephthalic acid.
  • the formulator is not limited to crosslinking T units deriving from dibasic acids, for example, tribasic crosslinking T units, inter alia, citrate, may be used to link the PA units of the present invention.
  • Examples of (PA) w (T) x compounds according to the present invention are obtained by condensation of dicarboxylic acids inter alia succinic acid, maleic acid, adipic acid, terephthalic acid, with polyalkylene polyamines inter alia diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine wherein the ratio of the dicarboxylic acid to polyalkyleneamine is from 1:0.8 to 1:1.5 moles, preferably a ratio of from 1:0.9 to 1:1.2 moles wherein the resulting crosslinked material has a viscosity in a 50% by weight, aqueous solution of more than 100 centipoise at 25°C.
  • dicarboxylic acids inter alia succinic acid, maleic acid, adipic acid, terephthalic acid
  • polyalkylene polyamines inter alia diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine
  • polyamines of the present invention are (PA) w (T) x units which are further crosslinked by L units to form polyamido amines having the formula [(PA) w (T) x ] y [L] z or are reacted with PA units to form non-amide polyamines having the formula (PA) w (L) z .
  • the L units of the present invention are any unit which suitably crosslinks PA units or (PA) w (T) x units.
  • Preferred L linking units comprise units which are derived from the use of epihalohydrins, preferably epichlorohydrin, as a crosslinking agent.
  • the epihalohydrins can be used directly with the PA units or suitably combined with other crosslinking adjuncts non-limiting examples of which include alkyleneglycols, and polyalkylene polyglycols inter alia ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol-1,6-glycerol, oligoglycerol, pentaerythrites, polyols which are obtained by the reduction of carbohydrates (sorbitol, mannitol), monosaccharides, disaccharides, oligosaccharides, polysaccharides, polyvinyl alcohols, and mixtures thereof.
  • alkyleneglycols and polyalkylene polyglycols inter alia ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol,
  • a suitable L unit is a dodecylene unit having the formula: -(CH 2 ) 12 - wherein an equivalent of 1,12-dichlorododecane is reacted, for example, with a suitable amount of a PA unit to produce a polyamine which is crosslinked via dodecylene units.
  • L crosslinking units which comprise only carbon and hydrogen are considered to be "hydrocarbyl" L units.
  • Preferred hydrocarbyl units are polyalkylene units have the formula: -(CH 2 ) n - wherein n is from 1 to about 50.
  • Hydrocarbyl L units may be derived from hydrocarbons having two units which are capable of reacting with the nitrogen of the PA units.
  • Non-limiting examples of precursors which result in the formation of hydrocarbyl L units include 1,6-dibromohexane, 1,8-ditosyloctane, and 1,14-dichlorotetradecane.
  • non-amide forming crosslinking L units are the units which derive from crosslinking units wherein epihalohydrin is used as the connecting unit.
  • 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the bis-epoxide non-amide forming L unit precursor having the formula: which when reacted with one or more PA units or (PA) w (T) x units results in an L crosslinking unit having the formula: however, it is not necessary to pre-form and isolate the bis-epoxide, instead the crosslinking unit precursor may be formed in situ by reaction of 1,12-dihydroxydodecane or other suitable precursor unit with epihalohydrin in the presence of grafted or ungrafted PA units or (PA) w (T) x units.
  • crosslinking L units which utilize one or more epihalohydrin connecting units include polyalkyleneoxy L units having the formula: wherein R 1 is ethylene, R 2 is 1,2-propylene, x is from 0 to 100 and y is from 0 to 100.
  • Another preferred unit which can comprise an L unit and which can be suitably combined with epihalohydrin connecting units include polyhydroxy units having the formula: wherein the index t is from at least 2 to about 20 and the index u is from 1 to about 6.
  • the formulator may also combine units to form hybrid L crosslinking units, for example, units having the formula: wherein the indexes w and y are each independently from 1 to 50, z is units are present in a sufficient to suitably connect the polyhydroxy units and the polyalkyleneoxy units into the backbone without the formation of ether linkages.
  • L linking group which comprises both a polyalkyleneoxy and a polyhydroxy unit.
  • a further example of a preferred crosslinking L units are units which comprises at least two aziridine groups as connecting groups, for example an L unit having the formula: which can be used to link two (PA) w units, two (PA) w (T) x units, or mixtures thereof.
  • the polyamines of the present invention may have varying final compositions, for example, (PA) w (T) x , [(PA) w (T) x ] y [L] z , [(PA)] w [L] z , and mixtures thereof, wherein each PA unit may be grafted or ungrafted.
  • the indices w and x have values such that the ratio of w to x is from 0.8 : 1 to 1.5 : 1; y and z have values such that said polyamido compound comprises from about 0.05, preferably to about 0.3 to 2 parts by weight of said L unit.
  • the indices w and y will be equal to 1 and x and z will be equal to 0.
  • the index y is equal to 1 and z is equal to 0.
  • the indices w and y are equal to 1 and x is equal to 0.
  • An preferred embodiment of the present invention which comprises PA units, T units, and L units includes the reaction product of:
  • the (PA) w (T) x polyamine compound may be partially amidated ("capped" as described herein above) by treatment with a mono carboxylic acid or the esters of mono carboxylic acids.
  • the formulator may vary the degree to which the backbone nitrogens are amidated according to the desired properties of the final Fabric Enhancement Polymer.
  • suitable mono-carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof.
  • the high molecular weight modified polyamine condensation products of the present invention are preferably formed from the reaction of one or more grafted, cross-linked polyethyleneimines and one or more polyethylene and/or polypropylene glycol copolymers, wherein the resulting crosslinked modified polyamines (resins) have a final viscosity of more than or equal to 300 mPa-sec., preferably from 400 to 2,500 mPa-sec. when measured at 20° C in a 20% aqueous solution.
  • the modified polyamine compounds of the present invention are suitably described in U.S. 3,642,572 Eadres et al., issued February 15, 1972 , U.S.
  • a further example of preferred polyamines according to the present invention are polyamines derived from amino acid residues.
  • the term "residue” is defined as "one unit which comprises the polymeric material of the present invention".
  • a non-limiting example of a residue which comprises the polymeric material is a lysine residue having the formula: wherein preferably said lysine residue forms the backbone of said polymeric material by forming a bond to the ⁇ -amino unit, however, the lysine residue may be suitably incorporated into the backbone via the ⁇ -amino unit; or an ornithine residue having the formula: wherein preferably said ornithine residue forms the backbone of said polymeric material by forming a bond to the ⁇ -amino unit, however, the ornithine residue may be optionally incorporated into the backbone via the ⁇ -amino unit; and said lysine residue or ornithine residue may have any optical isomer form, i.e., de
  • the amino acid-based polymers of the present invention comprise at least about 5% by weight of lysine, ornithine, or mixtures thereof, preferably at least about 10%, more preferably at least about 20%, most preferably at least about 40% by weight of lysine, ornithine, or mixtures thereof.
  • N-term and C-term are defined as an “amino terminating unit” and a “carboxyl terminating unit” respectively and are used throughout the present specification to indicate the capping units of the main polymeric chain as well as any branching chains.
  • the polymeric material of the present invention has the formula: N-term-[Lys] x -[Orn] y -[AA] z -C-term wherein Lys represents a residue of the amino acid lysine, Orn represents a residue of the amino acid ornithine, and AA represents a residue of a non-lysine or non-ornithine amino acid, carboxylic acid, or other chain propagating residue.
  • the lysine and ornithine residues are preferably incorporated into the polymeric chain via the ⁇ -amino residue and the carboxylate residue.
  • this "normal" incorporation does not preclude incorporation of a lysine or ornithine residue into the backbone or branch chain via two amino units whereby the carboxyl unit remains un-incorporated into any chain.
  • AA units are amino acid or other chain propagating residues having the formula: wherein the index n is from 0 to 10, preferably 1, 2 and 4; the preferred R units are independently selected from the group consisting of:
  • R 1 units are independently selected form the group consisting of:
  • N-term amino terminal capping groups terminate, truncate or end the amine terminus of the main polymeric chain or branch chains.
  • Preferred amino terminal capping groups are selected from the group consisting of:
  • C-term carboxy terminal capping groups terminate, truncate, or end the carboxy terminus of the main polymeric chain or branch chains.
  • Preferred carboxy terminal capping groups are selected from the group consisting of:
  • the polyamines which serve as carbonyl end units may serve to cap one or more carboxy terminal units of the same chain or two or more different chains.
  • the preferred polymer chains of the present invention have the amino terminus (N-term unit) of the main chain and branch chains capped with hydrogen and the carboxy terminus (C-term unit) of the main chain and branch chains capped with -OH.
  • the formulator may, preferably partially amidate the compounds of the present invention by treatment with a mono carboxylic acid or the esters of mono carboxylic acids.
  • the formulator may vary the degree to which the backbone nitrogens are amidated according to the desired properties of the final Fabric Enhancement Polymer.
  • suitable mono-carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof.
  • an amino acid having two amine moieties inter alia lysine, ornithine is co-condensed with caprolactam or aminocaproic acid to form a co-condensation product.
  • Other preferred co-condensates include reaction of lysine or ornithine with lauric acid to form the amidated polymer.
  • amino units of any lysine, ornithine, or AA unit may be optionally quaternized, preferably quaternized by one or more units selected from the group consisting of C 1 -C 4 linear or branched alkyl, benzyl, and mixtures thereof.
  • N-terminal or C-terminal capping units which have more than one functionality inter alia two carboxy units of a diacid (succinic acid), may crosslink two or more poly lysine or poly ornithine comprising chains. Therefore, in addition to capping, and therefore truncating the N-terminal ends of two separate polyamine backbones, a unit such as succinic acid may crosslink two polyamine chains.
  • the molecular weight of the amino acid-based polymeric materials of the present invention are preferably from about 400 daltons, more preferably from about 1000 daltons, most preferably from about 2000 daltons to preferably about 500,000 daltons, more preferably to about 25,000 daltons, most preferably to about 10,000 daltons.
  • polyamines of the present invention are the polyamines wherein the amine nitrogen is tethered to an alkylene backbone.
  • the following are non-limiting examples of tethered polymeric amines according to the present invention.
  • the tethered polymeric amines of the present invention have the general formula: wherein R' and R" are each independently hydrogen, C 1 -C 6 alkyl, phenyl, substituted phenyl, C 7 -C 22 alkylenearyl, and mixtures thereof, R 3 is an amine comprising unit, non-limiting examples of which include: -N(R) 2 , -N + (R) 3 , -C(O)N(R) 2 , -C(O)N + (R) 3 , and mixtures thereof; wherein R is hydrogen, C 1 -C 12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R 1 O) z Y, wherein R 1 is C 1 -C 6 linear or branched alkylene, Y is hydrogen or an anionic unit. Each cationic nitrogen will have an anionic unit X which provides charge neutrality to the polymer.
  • the index x is from about 5 to about 1,000,000 (one million
  • One class of tethered polymeric amines are the quaternized and non-quatemized polyvinylamines having the formula: wherein R is hydrogen, C 1 -C 12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R 1 O) z Y, wherein R 1 is C 1 -C 6 linear or branched alkylene, Y is hydrogen or an anionic unit, non-limiting examples of which include, -(CH 2 ) f CO 2 M, -C(O)(CH 2 ) f CO 2 M, -(CH 2 ) f PO 3 M, -(CH 2 ) f OPO 3 M, -(CH 2 ) f SO 3 M, -CH 2 (CHSO 3 M)-(CH 2 ) f SO 3 M, -CH 2 (CHSO 2 M)(CH 2 ) f SO 3 M, -C(O)CH 2 CH(SO 3 M)CO 2 M, -C(O)
  • the index x has the value from about 50 to about 1,500; preferably the index x has a value such that the resulting polymeric suds stabilizer has an average molecular weight of from about 2,500, preferably from about 10,000, more preferably from about 20,000 to about 150,000, preferably to about 90,000, more preferably to about 80,000 daltons.
  • One class of polymeric suds stabilizer according to the present invention are the alkyl acrylamides having the formula: wherein R is hydrogen, C 1 -C 12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R 1 O) z Y, wherein R 1 is C 1 -C 6 linear or branched alkylene, Y is hydrogen or an anionic unit, non-limiting examples of which include, -(CH 2 ) f CO 2 M, -C(O)(CH 2 ) f CO 2 M, -(CH 2 ) f PO 3 M, -(CH 2 ) f OPO 3 M, -(CH 2 ) f SO 3 M, -CH 2 (CHSO 3 M)-(CH 2 ) f SO 3 M, -CH 2 (CHSO 2 M)(CH 2 ) f SO 3 M, -C(O)CH 2 CH(SO 3 M)CO 2 M, -C(O)CH 2 CH(CO 2 M)
  • the index x has the value from about 50 to about 1,500; preferably the index x has a value such that the resulting polymer has an average molecular weight of from about 2,500, preferably from about 10,000, more preferably from about 20,000 to about 150,000, preferably to about 90,000, more preferably to about 80,000 daltons.
  • the ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a ⁇ 20 1b. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
  • PEI polyethyleneimine
  • Nippon Shokubai having a listed average molecular weight of 600 equating to about 0.417 moles of polymer and 6.25 moles of nitrogen functions
  • the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
  • the autoclave contents are heated to 130 °C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
  • the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
  • the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
  • Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure.
  • the autoclave is charged to 200 psia with nitrogen.
  • Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of approximately 5225 g of ethylene oxide (resulting in a total of 20 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
  • reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
  • the strong alkali catalyst is neutralized by adding 60 g methanesulfonic acid (0.625 moles).
  • the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
  • inert gas argon or nitrogen
  • the ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a ⁇ 20 1b. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
  • PEI polyethyleneimine
  • the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
  • the autoclave contents are heated to 130 °C while applying vacuum.
  • the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
  • the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
  • the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
  • Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure.
  • the autoclave is charged to 200 psia with nitrogen.
  • Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm.
  • 4500 g of ethylene oxide resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function
  • the temperature is increased to 110 °C and the mixture stirred for an additional hour.
  • Dimethyl sulfate (Aldrich, 8.48g, 0.067 mol) is added all at once to the rapidly stirring solution, which is then stoppered and stirred at room temperature overnight.
  • acetonitrile is evaporated on the rotary evaporator at ⁇ 60°C, followed by a Kugelrohr apparatus (Aldrich) at ⁇ 80°C to afford ⁇ 220g of the desired material as a dark brown viscous liquid.
  • a 13 C-NMR (D 2 O) spectrum shows the absence of a peak at ⁇ 58ppm corresponding to dimethyl sulfate.
  • a 1 H-NMR (D 2 O) spectrum shows the partial shifting of the peak at 2.5ppm (methylenes attached to unquaternized nitrogens) to ⁇ 3.ppm.
  • the laundry detergent compositions of the present invention comprise a surfactant system.
  • a required component of the surfactant system is one or more mid-chain branched alkyl sulfate surfactant, one or more mid-chain branched alkyl alkoxy sulfate surfactant, or one or more mid-chain branched aryl sulfonate surfactant,
  • Other anionic surfactants inter alia, non mid-chain branched sulphonates, sulphates, together with nonionic surfactants, cationic surfactants, surfactants, and ampholytic surfactants may comprise the balance of the surfactant system.
  • the total amount of surfactant present in the compositions is from about 0.01% by weight, preferably from about 0.1% more preferably from about 1% to about 60%, preferably to about 30% by weight, of said composition.
  • the surfactant systems of the present invention may comprise a mid-chain branched alkyl sulfate surfactant and/or a mid-chain branched alkyl alkoxy sulfate surfactant. Because mid-chain branched alkyl sulfate or alkyl alkoxy sulfate surfactants are not required when mid-chain branched aryl sulfonate surfactants are present, the surfactant system comprises from 0%, when present from 0.01%, preferably from about 0.1 % more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of the surfactant system.
  • mid-chain branched alkyl sulfate surfactants or mid-chain branched alkyl alkoxy sulfate surfactants comprise 100% of the surfactant system said surfactants will comprise up to 60% by weight of the final laundry detergent composition.
  • the mid-chain branched alkyl sulfate surfactants of the present invention have the formula: the alkyl alkoxy sulfates have the formula: wherein R, R 1 , and R 2 are each independently hydrogen, C 1 -C 3 alkyl, and mixtures thereof; provided at least one of R, R 1 , and R 2 is not hydrogen; preferably R, R 1 , and R 2 are methyl; preferably one of R, R 1 , and R 2 is methyl and the other units are hydrogen.
  • the total number of carbon atoms in the mid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactants is from 14 to 20; the index w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; provided w + x + y + z is from 8 to 14 and the total number of carbon atoms in a surfactant is from 14 to 20; R 3 is C 1 -C 4 linear or branched alkylene, preferably ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof.
  • a preferred embodiment of the present invention comprises from 1 to 3 units wherein R 3 is 1,2-propylene, 1,3-propylene, or mixtures thereof followed by the balance of the R 3 units comprising ethylene units.
  • Another preferred embodiment comprises R 3 units which are randomly ethylene and 1,2-propylene units.
  • the average value of the index m is at least about 0.01.
  • the surfactant system comprises mostly alkyl sulfates with a small amount of alkyl alkoxy sulfate surfactant. Some tertiary carbon atoms may be present in the alkyl chain, however, this embodiment is not desired.
  • M denotes a cation, preferably hydrogen, a water soluble cation, and mixtures thereof
  • water soluble cations include sodium, potassium, lithium, ammonium, alkyl ammonium, and mixtures thereof.
  • the preferred mid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactants of the present invention are “substantially linear” surfactants.
  • the term “substantially linear” is defined for the purposes of the present invention as “alkyl units which comprise one branching unit or the chemical reaction products which comprise mixtures of linear (non-branched) alkyl units and alkyl units which comprise one branching unit”.
  • chemical reaction products refers to the admixture obtained by a process wherein substantially linear alkyl units are the desired product but nevertheless some non-branched alkyl units are formed.
  • the preferred mid-chain branched alkyl sulfate and alkyl alkoxy sulfate surfactants comprise one methyl branch, preferably said methyl branch is not on the ⁇ , ⁇ , or the second to the last carbon atom.
  • the branched chains are a mixture of isomers.
  • the surfactant systems of the present invention may comprise a mid-chain branched aryl sulphonate surfactant. Because mid-chain branched aryl sulfonate surfactants are not required when mid-chain branched alkyl sulfate and/or alkyl alkoxy surfactants are present, the surfactant system comprises from 0%, when present from 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of the surfactant system. When the mid-chain branched aryl sulphonate surfactants comprise 100% of the surfactant system said mid-chain branched aryl sulphonate surfactants will comprise up to 60% by weight of the final laundry detergent composition.
  • the mid-chain branched aryl sulphonates of the present invention have the formula: wherein A is a mid-chain branched alkyl unit having the formula: wherein R and R 1 are each independently hydrogen, C 1 -C 3 alkyl, and mixtures thereof, provided at least one of R and R 1 is not hydrogen; preferably at least one R or R 1 is methyl; wherein the total number of carbon atoms in said alkyl unit is from 6 to 18. Some tertiary carbon atoms may be present in the alkyl chain, however, this embodiment is not desired.
  • the integer x is from 0 to 13.
  • the integer y is from 0 to 13.
  • the integer z is either 0 or 1, preferably 0.
  • R 2 is hydrogen, C 1 -C 3 alkyl, and mixtures thereof. Preferably R 2 is hydrogen.
  • M' denotes a water soluble cation with sufficient charge to provide neutrality, preferably hydrogen, a water soluble cation, and mixtures thereof.
  • water soluble cations include sodium, potassium, lithium, ammonium, alkyl ammonium, and mixtures thereof.
  • the preferred mid-chain branched aryl sulphonate surfactants of the present invention are “substantially linear aryl” surfactants.
  • the term “substantially linear aryl” is defined for the purposes of the present invention as "an alkyl unit which is taken together with an aryl unit wherein said alkyl unit preferably comprises one branching unit, however, a non-branched linear alkyl unit having an aryl unit bonded to the 2-carbon position as part of an admixture is included as a substantially linear aryl surfactant".
  • the preferred alkyl units do not have a methyl branch on the second to the last carbon atom.
  • the branched chains are a mixture of isomers.
  • the relative position of the aryl moiety is key to the functionality of the surfactant.
  • the aryl moiety is attached to the second carbon atom in the branched chain as illustrated herein below.
  • the preferred mid-chain branched aryl sulphonates of the present invention will comprise a mixture of branched chains.
  • R 1 is methyl
  • the index z is equal to 0
  • the sulphate moiety is para (1,4) to the branched alkyl substituent thereby resulting in a "2-phenyl aryl sulphonate" defined herein by the general formula:
  • 2-phenyl aryl sulphonates are formed as a mixture together with "3-phenyl aryl sulphonates" defined herein by the general formula:
  • the surfactant properties of the mid-chain branched aryl sulphonates of the present invention can be modified by varying the ratio of 2-phenyl to 3-phenyl isomers in the final surfactant mixture.
  • a convenient means for describing the relative amounts of isomers present is the "2/3 phenol index" defined herein as "100 times the quotient of the amount of 2-phenyl isomer present divided by the amount of the 3-phenyl isomer which is present". Any convenient means, NMR, inter alia, can be used to determine the relative amounts of isomers present.
  • a preferred 2/3 phenyl index is at least about 275 which corresponds to at least 2.75 times more 2-phenyl isomer present than the 3-phenyl isomer in the surfactant mixture.
  • the preferred 2/3-phenyl index according to the present invention is from about 275, more preferably from about 350, most preferably from about 500 to about 10,000, preferably to about 1200, more preferably to about 700.
  • mid-chain branched surfactants of the present invention will be a mixture of isomers and the composition of the mixture will vary depending upon the process which is selected by the formulator to make the surfactants.
  • the following admixture is considered to comprise a substantially linear mid-chain branched aryl sulphonate admixture according to the present invention.
  • reaction mixture is stirred an additional 1 hour at 20°C.
  • the reaction mixture is then added to 600g of a mixture of ice and water with stirring.
  • a 30% sulfuric acid solution (228.6 g).
  • the resulting two liquid phases are added to a separatory funnel.
  • the aqueous layer is removed and the organic phase is extracted twice with water (600 mL).
  • the organic layer is dried and the solvent removed in vacuo to yield 115.45 g of the desired alcohol mixture.
  • a portion of the alcohol mixture (100 g) is charged to a glass autoclave liner together with benzene (300 mL) and a shape selective zeolite catalyst (acidic mordenite catalyst Zeocat TM FM-8/25H) (20 g).
  • the glass liner is fitted into a stainless steel, rocking autoclave.
  • the autoclave system is purged twice with 250 psig N 2 , and then charged to 1000 psig N 2 . With mixing, the solution is heated to 170°C for 14-15 hours. After cooling, the reaction product is filtered to remove catalyst and concentrated by distilling off any excess benzene.
  • a mixture of a "lightly branched olefin mixture" is obtained.
  • a portion of the lightly branched olefin mixture (50 g) is charged to a glass autoclave liner.
  • Benzene (150 mL) and a shape selective zeolite catalyst (acidic mordenite catalyst Zeocat TM FM-8/25H) (10 g) are added.
  • the glass liner is placed inside a stainless steel, rocking autoclave.
  • the autoclave is purged twice with 250 psig N 2 , and then charged to 1000 psig N 2 . With mixing, the solution is heated to 195°C for 14-15 hours.
  • After cooling the reaction product is filtered to remove catalyst and concentrated by distilling off any excess benzene. A clear liquid product is obtained.
  • the product is distilled under vacuum (1-5 mm of Hg) to afford a fraction which distills from 95°C - 135°C containing the desired "lightly branched alkylbenzene" admixture.
  • the lightly branched alkylbenzene fraction is treated with a molar equivalent of SO 3 , the resulting product is neutralized with sodium methoxide in methanol, and the methanol evaporated to give a mid-chain branched aryl sulphonate surfactant admixture which can be directly used in the surfactant system of the present invention.
  • the laundry detergent compositions of the present invention may optionally comprise at least about 0.01% by weight, preferably from about 0.1% to about 90%, preferably to about 60% more preferably to about 30% by weight, of the surfactant system, a non mid-chain branched alkyl sulfate or non-mid chain branched aryl sulphonate surfactant.
  • a non mid-chain branched alkyl sulfate or non-mid chain branched aryl sulphonate surfactant may be chosen by the formulator.
  • Preferred categories of surfactants are selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof. Within each category of surfactant, more than one type of surfactant of surfactant can be selected.
  • surfactant is preferably present to the extent of from about 0.1% to 60 %, preferably to about 30% by weight of the composition.
  • Nonlimiting examples of surfactants useful herein include:
  • compositions of the present invention may be in any form inter alia liquid, granular, paste.
  • the formulator may will use different polyamine/branched surfactant combinations.
  • formulations of the present invention are not restricted to laundry compositions but can be any type of surfactant comprising cleaner, inter alia, rug shampoos, hard surface cleaners.
  • the formulations which benefit from the combination of polyamines and mid-chain branched surfactants include formulations which comprise:
  • Heavy Duty Granular compositions according to the present invention comprise:
  • HDG laundry detergent compositions will typically comprise more of anionic detersive surfactants.
  • the formulator may add more or less "non" mid-chain branched surfactants depending upon, inter alia, water hardness.
  • Neutral polyamines, PEI 1800 E7, PEI 600 E20, inter alia, are suitable for use in HDG formulations.
  • a zwitterionic polyamine may be preferred.
  • hardness relates to the amount of cations, calcium, inter alia, which are dissolved in the water and which tend to diminish the surfactancy and cleaning capacity of surfactants.
  • hard water is a relative term and for the purposes of the present invention, water having at least "12 grams per gallon water (gpg, "American grain hardness” units) of calcium ion” is defined as “high hardness” and water having at least "18 gpg of calcium ion” is defined as "very high hardness”.
  • the formulator will employ a polyamine having a greater number of anionic units on the tethering backbone modifications than the number of backbone cationic units. This net charge balance has the effect of ameliorating the negative interaction of the surfactant molecules with the hydrophilic soil active polymers in high water hardness conditions.
  • zwitterionic polymer useful in high water hardness compositions has the formula: wherein the backbone is a hybrid backbone comprising 5 cationic units and the backbone tethers which modify the polyamine comprise 7 anionic units.
  • a formulation which is capable of providing enhanced fabric benefits wherein the polyamine does not comprise an oxidized backbone comprises:
  • An example of a Heavy Duty Liquid (HDL) composition according to the present invention comprises:
  • HDL laundry detergent compositions will typically comprise more of a lesser amount of an anionic detersive surfactant and more nonionic surfactants. Therefore, in one preferred type of embodiment, the formulator may employ a zwitterionic polyamine having an equal number of anionic units as the number of cationic units or a greater number of cationic backbone units than the number of anionic units.
  • a non-limiting example of a nonionic surfactant suitable for use in the present invention has the formula: wherein R is C 7 -C 21 linear alkyl, C 7 -C 21 branched alkyl, C 7 -C 21 linear alkenyl, C 7 -C 21 branched alkenyl, and mixtures thereof.
  • R 1 is ethylene;
  • R 2 is C 3 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably R 2 is 1,2-propylene.
  • Nonionic surfactants which comprise a mixture of R 1 and R 2 units preferably comprise from about 4 to about 12 ethylene units in combination with from about 1 to about 4 1,2-propylene units. The units may be alternating, or grouped together in any combination suitable to the formulator.
  • the ratio of R 1 units to R 2 units is from about 4 : 1 to about 8 : 1.
  • an R 2 units i.e. 1,2-propylene
  • R 3 is hydrogen, C 1 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.
  • R 4 is hydrogen, C 1 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably hydrogen.
  • index m is equal to 2
  • index n must be equal to 0 and the R 4 unit is absent and is instead replaced by a -[(R 1 O) x (R 2 O) y R 3 ] unit.
  • the index m is 1 or 2, the index n is 0 or 1, provided that when m is equal to 1, n is equal to 1; and when m is 2 n is 0; preferably m is equal to 1 and n is equal to one, resulting in one - [(R 1 O) x (R 2 O) y R 3 ] unit and R 4 being present on the nitrogen.
  • the index x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10.
  • the index y is from 0 to about 10, preferably 0, however when the index y is not equal to 0, y is from 1 to about 4.
  • Preferably all of the alkyleneoxy units are ethyleneoxy units.
  • indices x and y are average values and the true values may range over several values depending upon the process used to alkoxylate the amides.
  • Suitable means for preparing the polyoxyalkylene alkylamide surface active agents of the present invention can be found in " Surfactant Science Series", Editor Martin Schick, Volume I, Chapter 8 (1967 ) and Volume XIX, Chapter 1 (1987 ) included herein by reference.
  • the clay soil removal laundry detergent compositions of the present invention may optionally comprise a bleaching system.
  • Bleaching systems typically comprise a "bleaching agent” (source of hydrogen peroxide) and an “initiator” or “catalyst”:
  • Bleaching Agents Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey) ", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms.
  • Sources of hydrogen peroxide which are suitable for use in the compositions of the present invention include, but are not limited to, perborates, percarbonates, perphosphates, persulfates, and mixtures thereof.
  • Preferred sources of hydrogen peroxide are sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and sodium persulfate, more preferably are sodium perborate monohydrate, sodium perborate tetrahydrate, and sodium percarbonate.
  • the source of hydrogen peroxide is present at a level of from about 40%, preferably from about 50%, more preferably from about 60% to about 100%, preferably to about 95%, more preferably to about 80% by weight, of the bleaching system.
  • Embodiments which are bleach comprising pre-soak compositions may comprise from 5% to 99% of the source of hydrogen peroxide.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
  • the source of hydrogen peroxide (peroxygen bleach component) in the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition.
  • bleach activators will comprise from about 0.1% to about 60% by weight, of the beaching system.
  • said composition comprises 60% by weight, of an activator (the maximal amount) and said composition (bleaching composition, laundry detergent, or otherwise) comprises 15% by weight of said activator (the maximal amount by weight)
  • said composition will comprise 25% by weight of a bleaching system (60% of which is bleach activator, 40% a source of hydrogen peroxide).
  • this is not meant to restrict the formulator to a 60:40 ratio of activator to hydrogen peroxide source.
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1:1, preferably from about 20:1, more preferably from about 10:1 1 to about 1:1, preferably to about 3:1.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C 10 -OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C 8 -OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam, Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
  • Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) amino hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS) an example of which is described in U.S. Patent No. 5,523,434 , dodecanoyloxybenzenesulphonate (LOBS or C 12 -OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C 11 -OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid (DOBA).
  • NOBS nonanoyloxybenzenesulphonate
  • NACA-OBS 4-[N-(nonaoyl) amino hexanoyloxy]-benzene sulfonate sodium salt
  • DOBA decanoyloxybenzoic acid
  • Preferred bleach activators are those described in U.S. 5,698,504 Christie et al., issued December 16, 1997 ; U.S. 5,695,679 Christie et al. issued December 9, 1997 ; U.S. 5,686,401 Willey et al., issued November 11, 1997 ; U.S. 5,686,014 Hartshorn et al., issued November 11, 1997 ; U.S. 5,405,412 Willey et al., issued April 11, 1995 ; U.S. 5,405,413 Willey et al., issued April 11, 1995 ; U.S. 5,130,045 Mitchel et al., issued July 14, 1992 ; and U.S.
  • Quaternary substituted bleach activators may also be included.
  • the present cleaning compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA quaternary substituted bleach activator
  • QSP quaternary substituted peracid
  • Preferred QSBA structures are further described in U.S. 5,686,015 Willey et al., issued November 11, 1997 ; U.S. 5,654,421 Taylor et al., issued August 5, 1997 ; U.S. 5,460,747 Gosselink et al., issued October 24, 1995 ; U.S. 5,584,888 Miracle et al., issued December 17, 1996 ; and U.S. 5,578,136 Taylor et al., issued November 26, 1996 ; all of which are incorporated herein by reference.
  • bleach activators useful herein are amide-substituted as described in U.S. 5,698,504 , U.S. 5,695,679 , and U.S. 5,686,014 each of which are cited herein above.
  • Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.
  • bleaching results can be obtained from bleaching systems having with in-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5.
  • activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffering agents can be used to secure such pH.
  • the laundry detergent compositions of the present invention optionally comprises a bleaching system which contains one or more bleach catalysts.
  • Selected bleach catalysts inter alia 5,12-dimethyl-1,5,8,12-tertaaza-bicyclo[6.6.2]hexadecane manganese (II) chloride maybe formulated into bleaching systems which do not require a source of hydrogen peroxide or peroxygen bleach.
  • compositions comprise from about 1 ppb (0.0000001 %), more preferably from about 100 ppb (0.00001%), yet more preferably from about 500 ppb (0.00005%), still more preferably from about 1 ppm (0.0001%) to about 99.9%, more preferably to about 50%, yet more preferably to about 5%, still more preferably to about 500 ppm (0.05%) by weight of the composition, of a transition-metal bleach catalyst
  • Non-limiting examples of suitable manganese-based catalysts are disclosed in U.S. 5,576,282 Miracle et al., issued November 19, 1996 ; U.S. 5,246,621 Favre et al., issued September 21, 1993 ; U.S. 5,244,594 Favre et al., issued September 14, 1993 ; U.S. 5,194,416 Jureller et al., issued March 16, 1993 ; U.S. 5,114,606 van Vliet et al., issued May 19, 1992 ; U.S. 4,430,243 Bragg, issued February 7, 1984 ; U.S. 5,114,611 van Kralingen, issued May 19, 1992 ; U.S. 4,728,455 Rerek, issued March 1, 1988 ; U.S.
  • Non-limiting examples of suitable cobalt-based catalysts are disclosed in U.S. 5,597,936 Perkins et al., issued January 28, 1997 ; U.S. 5,595,967 Miracle et al., issued January 21, 1997 ; U.S. 5,703,030 Perkins et al., issued December 30, 1997 ; U.S. Patent 4,810,410 Diakun et al, issued March 7,1989 ; M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94 ; J. Chem. Ed. (1989), 66 (12), 1043-45 ; The Synthesis and Characterization of Inorganic Compounds, W.L.
  • bleach catalysts are described in WO 98/39406 A1 published September 11, 1998 and included herein by reference. Suitable examples of these bleach catalysts include:
  • the bleaching systems of the present invention may optionally further comprise from 0.1%, preferably from 1%, more preferably from 5% to about 10%, preferably to about 7% by weight, of one or more pre-formed bleaching agents.
  • Pre-formed bleaching materials typically have the general formula: wherein R is a C 1 -C 22 alkylene, C 1 -C 22 substituted alkylene, phenylene, C 6 -C 22 substituted phenylene, and mixtures thereof, Y is hydrogen, halogen, alkyl, aryl, -C(O)OH, -C(O)OOH, and mixtures thereof.
  • the organic percarboxylic acids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
  • the organic percarboxylic acid is aliphatic, the unsubstituted acid has the general formula: wherein Y can be hydrogen, methyl, methyl chloride, carboxylate, percarboxylate; and n is an integer having the value from 1 to 20.
  • the unsubstituted acid has the general formula: wherein Y can be hydrogen, alkyl, haloalkyl, carboxylate; percarboxylate, and mixtures thereof.
  • Typical monoperoxy percarboxylic acids useful herein include alkyl percarboxylic acids and aryl percarboxylic acids such as:
  • compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material.
  • a chlorine-type bleaching material include for example sodium dichloroisocyanurate (“NaDCC").
  • NaDCC sodium dichloroisocyanurate
  • chlorine-type bleaches are less preferred for compositions which comprise enzymes.
  • adjunct ingredients useful in the laundry compositions of the present invention
  • said adjunct ingredients include builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
  • the laundry detergent compositions of the present invention preferably comprise one or more detergent builders or builder systems.
  • the compositions will typically comprise at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably to about 30% by weight, of detergent builder.
  • 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 about 1% builder. Formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-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), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence pf 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 alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in. U.S. 4,664,839 Rieck, issued May 12, 1987 .
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate.
  • 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 O 2x+1 ⁇ yH 2 O 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.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na 2 SiO 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 stabilizing 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: [M z (zAlO 2 ) y ] ⁇ xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • 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. 3,985,669, Krummel et al, issued October 12, 1976 . Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 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 neutralized 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 polycarboxylates, including oxydisuccinate, as disclosed in U.S. 3,128,287 Berg, issued April 7, 1964 , and U.S. 3,635,830 Lamberti et al., issued January 18, 1972 . See also "TMS/TDS" builders of U.S. 4,663,071 Bush et al., issued May 5, 1987 .
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 3,923,679 Rapko, issued December 2, 1975 ; U.S.
  • 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
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxy-disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic 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 C 5 -C 20 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 European Patent Application 86200690.5 / 0,200,263 , published November 5, 1986.
  • Fatty acids e.g., C 12 -C 18 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.
  • polymeric dispersing agents which include polymeric polycarboxylates and polyethylene glycols, are suitable for use in the present invention.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in U.S. 3,308,067 Diehl, issued March 7, 1967 .
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000, preferably from about 5,000, more preferably from about 7,000 to 100,000, more preferably to 75,000, most preferably to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982 , as well as in EP 193,360, published September 3, 1986 , which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
  • Such materials are also disclosed in EP 193,360 , including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • compositions according to the present invention may optionally comprise one or more soil release agents.
  • soil release agents will generally comprise from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition.
  • Polymeric soil release agents are characterized 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 the laundry cycle and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occuring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the present invention further relates to a method for removing hydrophilic soils form fabric, preferably clothing, said method comprising the step of contacting fabric in need of cleaning with an aqueous solution of a laundry detergent composition comprising:
  • the aqueous solution comprises at least about 0.01% (100 ppm), preferably at least about 1% (1000 ppm)by weight, of said laundry detergent composition.
  • compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. 5,691,297 Nassano et al., issued November 11, 1997 ; U.S. 5,574,005 Welch et al., issued November 12, 1996 ; U.S. 5,569,645 Dinniwell et al., issued October 29, 1996 ; U.S. 5,565,422 Del Greco et al., issued October 15, 1996 ; U.S. 5,516,448 Capeci et al., issued May 14, 1996 ; U.S. 5,489,392 Capeci et al., issued February 6, 1996 ; U.S. 5,486,303 Capeci et al., issued January 23, 1996 all of which are incorporated herein by reference.
  • compositions according to the present invention TABLE I weight % Ingredients 6 7 8 Branched alkyl sulfate 1 . 10.0 10.0 10.0 Branched aryl sulphonate 2 -- 10.0 -- Sodium C 12 -C 15 alcohol sulfate 10.0 -- -- Sodium linear alkylbenzene sulphonate -- -- 10.0 Sodium C 12 -C 15 alcohol ethoxy (1.8) sulfate 1.0 -- -- Cationic surfactant 3 0.5 0.5 -- Nonionic surfactant 4 0.63 0.63 -- Polyamine 5 0.3 0.5 0.5 Sodium carbonate 25.0 17.0 25.0 Builder 6 25.0 20.0 20.0 Protease enzyme 7 .
  • Balance to 100% can, for example, include minors like optical brightener, perfume, suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO 3 , talc, silicates, etc.
  • Balance to 100% can, for example, include minors like optical brightener, perfume, suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO 3 , talc, silicates, etc.
  • Table IV Weight % Ingredients 15 16 17 18 Sodium C 11 -C 13 alkylbenzenesulfonate 15.00 14.45 6.00 10.00 C 12 -C 14 Dimethyl hydroxyethyl quaternary amine 0.40 0.40 -- -- C 9 -C 14 Dimethyl hydroxyethyl quaternary amine -- -- 1.0 1.0 C 14 -C 15 Alcohol ethoxylate (3) sulfate -- -- 1.00 1.00 Branched alkyl sulfate 1 12.00 10.00 12.00 10.00 Polyamine 2 0.50 0.50 0.50 0.50 Sodium tripolyphosphate 28.00 25.00 20.00 24.00 Zeolite 12.00 14.50 -- -- CMC 1.10 1.10 0.50 0.50 Soil Release Agent 3 0.15 0.15 0.
  • Balance to 100% can, for example, include minors like optical brightener, perfume, suds suppresser, soil dispersant, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO 3 , talc, silicates, etc.
  • Ingredients 22 23 24 Branched alkyl sulfate 1 10.0 -- 10.0 Branched aryl sulphonate 2 -- 10.0 10.0 Sodium C 12 -C 15 alcohol sulfate 10.0 10.0 -- Sodium C 12 -C 15 alcohol ethoxy (1.8) sulfate 1.0 -- -- Sodium C 12 -C 15 alcohol ethoxy (2.25) sulfate -- 1.0 -- Cationic surfactant 3 -- -- 0.70
  • Nonionic surfactant 4 15.0 15.0 20.0 Polyamine 5
  • Solvent 6 15.0 15.0 10.0 Sodium carbonate 10.0 10.0 7.0 Builder 7 8.0 10.0 10.0 Protease enzyme 8 0.70 -- -- Protease enzyme 9 -- 0.70 -- Protease enzyme 10
  • Balance to 100% can, for example, include minors like optical brightener, perfume, suds suppressor, soil dispersant, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO 3 , talc, silicates, etc.
  • TABLE VII weight % Ingredients 25 26 27 Branched alkyl sulfate 1 10.0 -- 20.0 Branched aryl sulphonate 2 -- 20.0 -- Sodium C 12 -C 15 alcohol sulfate 10.0 -- -- Sodium linear alkylbenzene sulphonate -- 10.0 -- Sodium C 12 -C 15 alcohol ethoxy (1.8) sulfate -- -- 1.0 Cationic surfactant 3 -- 0.50 -- Nonionic surfactant 4 17.0 17.0 10.0 Polyamine 5 1.00 0.50 0.75 Solvent 6 20.0 18.0 20.0 Sodium carbonate -- 12.0 -- Builder 7 10.0 8.0 6.0 Protease enzyme 8 0.70 -- -- Protease enzyme 9 -- -- 0.70 Protease enzyme 10 -- -- 1

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Claims (2)

  1. Waschmittelzusammensetzung, umfassend:
    a) von 0,01 Gew.-% ein Polyamin mit der Formel:
    Figure imgb0056
     worin R-Einheiten die Formel -(R2O)wR3- aufweisen, worin R2 und R3 jeweils unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus linearem C2-C8-Alkylen, verzweigtem C3-C8-Alkylen, Phenylen, substituiertem Phenylen und Mischungen davon; R2-Einheiten jeweils Ethylen sind; Y Wasserstoff, -SO3M und Mischungen davon ist; der Index t 15 bis 25 ist; der Index m von 0 bis 20 ist; der Index w von 1 bis 10 ist und Q eine Quatemisierungseinheit ist, die ausgewählt ist aus der Gruppe, bestehend aus linearem C1-C4-Alkyl, Benzyl und Mischungen davon;
    b) von 0,01 Gew.-% ein Tensidsystem, umfassend:
    i) von 1 Gew.-% bis 100 Gew.-% des Tensidsystems ein verzweigtes Mittelketten-Alkylsulfattensid, ausgewählt aus der Gruppe, bestehend aus Tensiden mit der Formel:
    Figure imgb0057
     der Formel:
    Figure imgb0058
     und Mischungen davon; worin R, R1 und R2 jeweils unabhängig Wasserstoff, C1-C3-Alkyl und Mischungen davon sind, mit der Maßgabe, dass die Gesamtzahl an Kohlenstoffatomen in dem Tensid 14 bis 20 beträgt und mindestens einer der Reste R, R1 und R2 kein Wasserstoff ist; der Index w eine ganze Zahl von 0 bis 13 ist; x eine ganze Zahl von 0 bis 13 ist; y eine ganze Zahl von 0 bis 13 ist; z eine ganze Zahl von mindestens 1 ist; mit der Maßgabe, dass w + x + y + z von 8 bis 14 ist und die Gesamtzahl an Kohlenstoffatomen in einem Tensid von 14 bis 20 beträgt; R3 Ethylen, 1,2-Propylen, 1,3-Propylen, 1,2-Butylen, 1,4-Butylen und Mischungen davon ist; der Durchschnittswert des Indexes m mindestens 0,01 beträgt;
    ii) optional von 0,01 Gew.-% ein Tensid, das ausgewählt ist aus der Gruppe, bestehend aus anionischen, nichtionischen, kationischen, zwitterionischen, ampholytischen Tensiden und Mischungen davon; und
    c) zu übrigen Teilen Träger und Zusatzbestandteile.
  2. Zusammensetzung nach Anspruch 1, ferner von 1 Gew.-% ein Persauerstoff-Bleichsystem aufweisend, das Folgendes umfasst:
    i) zu 40 Gew.-% des Bleichsystems eine Wasserstoffperoxidquelle;
    ii) wahlweise von 0,1 Gew.-% des Bleichsystems einen Bleichaktivator;
    iii) wahlweise von 1 ppb der Zusammensetzung einen Übergangsmetall-Bleichkatalysator; und
    iv) wahlweise von 0,1 Gew.-% ein vorab gebildetes Persauerstoff-Bleichmittel.
EP00947338A 1999-07-16 2000-07-13 Polyamine und mittelseitenkettige tenside enthaltende wäschewaschmittelzusammensetzungen Expired - Lifetime EP1196525B1 (de)

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CN1681913A (zh) 2002-09-12 2005-10-12 宝洁公司 聚合物体系及包含同样物质的清洁组合物
DE10354561A1 (de) * 2003-11-21 2005-07-14 Henkel Kgaa Lösliches Buildersystem
EP3109306A1 (de) * 2015-06-22 2016-12-28 The Procter and Gamble Company Lösungsmittelarme flüssige reinigungsmittelzusammensetzungen
WO2017079959A1 (en) 2015-11-13 2017-05-18 The Procter & Gamble Company Detergent compositions
WO2017079961A1 (en) 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing branched alkyl sulfate surfactant with little or no alkoxylated alkyl sulfate
ES2794400T5 (es) 2015-11-13 2023-07-04 Procter & Gamble Composiciones de limpieza que contienen un tensioactivo de tipo alquilsulfonato ramificado y un tensioactivo no iónico de cadena corta
JP6591278B2 (ja) * 2015-12-15 2019-10-16 花王株式会社 食器用固体洗浄剤組成物
FR3045344B1 (fr) * 2015-12-21 2019-09-27 L'oreal Utilisation de composes polyamines particuliers en presence d'oxydants pour traiter les fibres keratiniques
EP3208260A1 (de) * 2016-02-17 2017-08-23 Clariant International Ltd Alkoxylierte hydroxybenzoesäureester oder amide
WO2018127390A1 (en) * 2017-01-06 2018-07-12 Unilever N.V. Stain removing composition

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AU6096800A (en) 2001-02-05
BR0012507B1 (pt) 2012-06-26
CN100529040C (zh) 2009-08-19
BR0012507A (pt) 2002-04-02
CA2378903C (en) 2010-02-09
WO2001005924A1 (en) 2001-01-25
JP2003505536A (ja) 2003-02-12
ATE432971T1 (de) 2009-06-15
CN1374997A (zh) 2002-10-16
EP1196525A1 (de) 2002-04-17
JP5085000B2 (ja) 2012-11-28
MXPA02000634A (es) 2002-07-02
DE60042330D1 (de) 2009-07-16
CA2378903A1 (en) 2001-01-25

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