WO2000022079A1 - Detergent compositions or components - Google Patents

Detergent compositions or components Download PDF

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Publication number
WO2000022079A1
WO2000022079A1 PCT/US1999/023147 US9923147W WO0022079A1 WO 2000022079 A1 WO2000022079 A1 WO 2000022079A1 US 9923147 W US9923147 W US 9923147W WO 0022079 A1 WO0022079 A1 WO 0022079A1
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WO
WIPO (PCT)
Prior art keywords
group
alkyl
acid
independently
weight
Prior art date
Application number
PCT/US1999/023147
Other languages
French (fr)
Inventor
Gabor Heltovics
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9905474A external-priority patent/GB2347680A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to US09/807,388 priority Critical patent/US6472364B1/en
Priority to AU12007/00A priority patent/AU1200700A/en
Priority to BR9914505-7A priority patent/BR9914505A/en
Priority to EP99970415A priority patent/EP1121409A1/en
Priority to CA002346292A priority patent/CA2346292A1/en
Priority to JP2000575973A priority patent/JP2003530440A/en
Publication of WO2000022079A1 publication Critical patent/WO2000022079A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0671—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having halogen atoms linked directly to the Pc skeleton
    • 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
    • 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
    • C11D1/62—Quaternary ammonium 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof

Definitions

  • the present invention relates to compositions or components composing certain cyclic amme based polymers and certain anionic cellulose mate ⁇ als
  • the present invention relates to a detergent composition or component or additive compnsing: a) from 0.01% to 90% by weight, preferably from 0.05% to 50% by weight, of a salt of an anionic cellulose matenal compnsing an anionic substituent group
  • R - X - Z wherein R is a saturated , unsaturated or aromatic hydrocarbon spacer group, X is oxygen, nitrogen or sulphur, Z is carboxylate, sulphonate, sulphate or phosphonate group: and b) from 0.01% to 90% by weight, preferably from about 0.05% to about 20% by weight of a cyclic amme based polymer.
  • the present invention also relates to the launde ⁇ ng or treating of fabncs and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions or components descnbed herein, or formed from the individual polymenc mate ⁇ als of such compositions or components.
  • Launde ⁇ ng of fabncs and textiles in such washing solutions imparts fabric appearance benefits to the fabnc and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifadmg, improved abrasion resistance, and/or enhanced softness and also improved whiteness and/ or bnghtness maintenance or even improved cleaning performance
  • the cyclic amine based polymers and the cellulose matenal are preferably in an intimate mixture with one another. In one preferred embodiment, the compounds are intimately mixed pnor to introduction to the composition or component of the invention.
  • the mixture is present in an agglomerated, compacted or spray-d ⁇ ed particle, when the composition or component is solid.
  • the compounds are mixed with an anionic surfactant, preferably LAS. as described herein after. It may also be preferred that a hydrotrope is admixed to this mixture, preferably STS Also preferably present in the mixture are inorganic and/or organic salts and acids and or silicates or alummosihcates, including zeolite, amorphous silicates, crystalline layered silicates, carbonate, bicarbonate, phosphate, citnc acid, malic acid, maleic acid, tarta ⁇ c acid or salts thereof, or mixtures of these ingredients
  • compositions or components of the present invention comp ⁇ se one or more cyclic amine based polymer.
  • 'polymers' include not only polymers, but also ohgomers, co-polymers, co- ohgomers, present in any structural arrangement, also including cross-linked arrangements.
  • an ohgomer is a molecule consisting of only a few monomer units while polymers comp ⁇ se considerably more monomer units.
  • ohgomers are defined as molecules having an average molecular weight below about 1 ,000 and polymers are molecules having an average molecular weight of greater than about 1 ,000, copolymers or co-oligomers are mate ⁇ als wherein two or more dissimilar monomers have been simultaneously or sequentially polymenzed.
  • Copolymers or co-oligomers of the present invention can include, for example, polymers or ohgomers polymenzed from a mixture of a primary cyclic amme based monomer, e.g., piperadine, and a secondary cyclic amme monomer, e.g., morphohne.
  • a primary cyclic amme based monomer e.g., piperadine
  • a secondary cyclic amme monomer e.g., morphohne.
  • the amount of cyclic amine based polymer may very.
  • the cyclic amine based polymers herein will generally be about 0.01% to about 90% by the weight of the detergent composition or component, more preferably from 0.05% to 20% or even from 0.05% to 15% by weight.
  • the polymer is present at a level of from 0.05% to 10% by weight of the detergent composition, preferably from 0.05% to 5% or even from 0.05% to 3% or even 0 1% to 2% by weight.
  • the polymer may preferably be present at a level of 0.05% to 40% by weight or even from 0.05% to 20% or even 0.1% to 15% or even 1 % to 10% by weight.
  • the cyclic amine based polymer herein is preferably present in the composition or component m such an amount that the concentration of cyclic amme m the wash is from 100 ppm to 10,000 ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm
  • the preferred cyclic amine based polymers herein can be charactenzed by the following general formula
  • each T is independently selected from the group consisting of H, C ⁇ -C ⁇ 2 alkyl, substituted alkyl,
  • W compnses at least one cyclic constituent selected from the group consisting of:
  • W may also comp ⁇ se an aliphatic or substituted aliphatic moiety of the general structure
  • each B is independently CJ-CJ alkylene.
  • each D is independently C 2 -Cg alkylene
  • each Q is independently selected from the group consisting of hydroxy, Ci -Cig alkoxy, C -C ⁇ g hydroxyalkoxy, ammo, C j -Ci alkylammo, dialkylamino, t ⁇ alkylamino groups, heterocyclic monoamino groups and diamino groups;
  • each Rj is independently selected from the group consisting of H, Ci-Cg alkyl and Cj-Cg hydroxyalkyl;
  • each R 2 is independently selected from the group consisting of C] -C ⁇ 2 alkylene, CJ -CJ 2 alkenylene, -CH 2 -CH(OR ⁇ )-CH 2 , Cg-Cj 2 alkarylene, C4- 2 dihydroxyalkylene, poly(C 2 -C 4 alkyleneoxy)alkylene, H 2 CH(OH)CH 2 OR 2 OCH 2 CH(OH)CH 2 -, and C3- C ⁇ 2 hydrocarbyl moieties; provided that when R 2 is a C 3 -C ⁇ 2 hydrocarbyl moiety the hydrocarbyl moiety can compnse from about 2 to about 4 branching moieties of the general structure: OH
  • R 3 is independently selected from the group consisting of H, O, R 2 , C]A20 hydroxyalkyl, C j -C 2 o alkyl, substituted alkyl, Cg-Cj ⁇ aryl, substituted aryl, C7-C1 1 alkylaryl, C I -C 2 Q ammoalkyl, -(CH 2 ) h COOM, -(CH 2 ) h SO 3 M, CH 2 CH(OH)SO 3 M, -(CH 2 )hOSO 3 M,
  • each R4 is independently selected from the group consisting of H, Cj-C 2 alkyl, Cj-C hydroxyalkyl, aryl and C -C 22 alkylaryl;
  • -each R5 is independently selected from the group consisting of C 2 -Cg alkylene, C -Cg alkyl substituted alkylene;
  • A is a compatible monovalent or di or polyvalent anion
  • the cyclic amme based polymer may comp ⁇ se combinations of these cyclic amine based materials.
  • a mixture of piperadine and epihalohydrin condensates can be combined with a mixture of morpholine and epihalohydrin condensates to achieve the desired fabric treatment results.
  • the molecular weight of cyclic polymers can vary within the mixture as is illustrated herein.
  • Preferred compounds that fall within this general structure include compounds: - wherein each R ⁇ is H; and -at least one W is selected from the group consisting of:
  • -at least one W is selected from the group consisting of:
  • -at least one W is selected from the group consisting of:
  • Preferred compounds to be used as the linking group R 2 include, but are not limited to. polyepoxides, ethylenecarbonate, propylenecarbonate, urea, ⁇ , ⁇ -unsaturated carboxylic acids, esters of ⁇ , ⁇ -unsaturated carboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids, anhydrides of ⁇ , ⁇ -unsaturated carboxylic acids, di- or polycarboxyhc acids, esters of di- or polycarboxyhc acids, amides of di- or polycarboxyhc acids, anhyd ⁇ des of di- or polycarboxyhc acids, glycidylhalogens, chloroformic esters, chloroacetic esters, denvatives of chloroformic esters, denvatives of chloroacetic esters, epihalohydnns, glycerol dichlorohyd ⁇ ns, bis- (halohyd ⁇ n
  • R 2 can also compnse a reaction product formed by reacting one or more of polyetherdiamines, alkylenediammes. polyalkylenepolyammes, alcohols, alkyleneglycols and polyalkyleneglycols with ⁇ , ⁇ -unsaturated carboxylic acids, esters of ⁇ , ⁇ - unsaturated carboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids and anhydrides of ⁇ , ⁇ - unsaturated carboxylic acids provided that the reaction products contain at least two double bonds, two carboxylic groups, two amide groups or two ester groups.
  • cyclic amme based polymers for use herein include adducts of two or more compositions selected from the group consisting of piperazme, piperadine. epichlorohydnn, epichlorohydnn benzyl quat, epichlorohydnn methyl quat, morphohne and mixtures thereof.
  • Imidazole-epi chlorohyd ⁇ n copolymers Highly preferred cyclic amme based polymers herein are referred to as Imidazole-epi chlorohyd ⁇ n copolymers.
  • cyclic amine based polymers can be linear or branched.
  • One specific type of branching can be introduced using a polyfunctional crosslinking agent.
  • An example of such such polymer is exemplified below.
  • compositions or components herein comp ⁇ se a salt of an anionic cellulose mate ⁇ al comprising an anionic substituent group R - X - Z wherem R is a saturated , unsaturated or aromatic hydrocarbon spacer group, X is oxygen, nitrogen or sulphur, Z is carboxylate, sulphonate, sulphate or phosphonate group.
  • the hydrocarbon spacer group is preferably a C
  • T e spacer group may also be substituted with one or more hydroxy groups.
  • the group X is preferably a nitrogen, or even more preferably an oxygen atom.
  • the group Z is preferably a carboxylate group.
  • the cation of the salt is preferably a potassium ion or more preferably a sodium ion.
  • the anionic cellulose mate ⁇ al herein will generally be about 0.01% to about 90% by the weight of the detergent composition or component, more preferably from 0.05% to 50% or even from 0.05% to 20%.
  • the mate ⁇ al is present at a level of from 0.05% to 10% by weight of the detergent composition, preferably from 0.05% to 7% or even from 0.05% to 5% or even 0.5% to 3%.
  • the matenal may preferably be present at a level of 0.05% to 40% by weight of the component, or even from 0.05% to 20% or even 0.1% to 15% or even l% to 10%.
  • the anionic cellulose material herein is preferably present in the composition or component in such an amount that the concentration of cyclic amme in the wash is from 100 ppm to 10,000 ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm.
  • compositions or components of the invention are preferably laundry, compositions, preferably in the form of granules, extrudates, flakes or tablets, liquids or pastes.
  • compositions or components in accord with the invention may also contain additional detergent components.
  • additional detergent components The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
  • They preferably contain one or more additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, additional organic polymeric compounds, including dispersants, soil suspension and anti-redeposition agents soil releasing agents, enzymes, suds suppressors, lime soap, , perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, additional organic polymeric compounds, including dispersants, soil suspension and anti-redeposition agents soil releasing agents, enzymes, suds suppressors, lime soap, , perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • Preferred additional ingredients are hydrophobically modified ether and ester cellulosic polymers as descnbed in co-pending application PCT US98/19139 and PCT/US98/19142. These polymers may be present at a level of from 0.01% to 10% by weight of the composition, more preferably at a level of from 0.05% to 5% by weight or even form 0.1 % to 2% by weight of the composition, or at a level of from 0.05% to 30% by weight of the component, more preferably at a level of from 0.1 % to 20% by weight or even form 0.3%) to 10%o by weight of the component.
  • compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the components or compositions in accord with the present invention preferably comprise an additional anionic surfactant.
  • any anionic surfactants useful for detersive purposes can be comprised in the detergent components or compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate and sulfonate surfactants are preferred.
  • surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, --C, monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C---C, . diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C J O-C I g alkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ 5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 1- Ci 8, most preferably C ⁇ 1- 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic Sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxyhc acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00"M + wherein R is a to Cj g alkyl group, x ranges from O to 10, and the ethoxvlate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a C to C1 g alkyl group, x is from 1 to 25, R j and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l -undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressers.
  • Suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
  • RJ (RJ ) CH2 COOM, wherein R is a C5-Cj 7 linear or branched alkyl or alkenyl group, R ⁇ is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-Cj 7 linear or branched alkyl or alkenyl group
  • R ⁇ is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ⁇ CONR ⁇ Z wherein : Rl is H, -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C ⁇ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably
  • Suitable fatty acid amide surfactants include those having the formula: R6C0N(R )2 wherein R is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R' is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula:
  • R- is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R ⁇ (OR ⁇ ) x N ⁇ (R ⁇ )2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Cjo-Ci g alkyl dimethylamine oxide, and C J Q-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent components or compositionss in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2COO ⁇ wherein R is a Cg-Ci g hydrocarbyl group, each R* is typically C1-C3 alkyl, and R ⁇ is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ 2-18 dimethyl-ammonio hexanoate and the 10- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono Cg- C ⁇ , preferably C ⁇ -Cio N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • cationic ester surfactants Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (i.e.
  • spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included.
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • cationic mono-alkoxylated amine surfactant preferably of the general formula I:
  • ⁇ is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms;
  • R ⁇ and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R ⁇ and R are methyl groups;
  • R ⁇ is selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and
  • p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
  • Particularly preferred ApR ⁇ groups are — CH 2 CH 2 OH, — CH 2 CH 2 CH 2 OH, — CH 2 CH(CH 3 )OH and — CH(CH 3 )CH 2 OH, with— CH2CH2OH being particularly preferred.
  • Preferred R 1 groups are linear alkyl groups. Linear Rl groups having from 8 to 14 carbon atoms are preferred.
  • Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
  • R! is Cj ⁇ -Ci hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C 10 and Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2 ⁇ ] and [CH2CH(CH3 ⁇ ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and or Pr and/or i-Pr units.
  • the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2%) to 7%, most preferably from 0.3%> to 3.0% by weight of the composition.
  • the cationic bis-alkoxylated amine surfactant preferably has the general formula II:
  • R! is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R ⁇ is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R ⁇ and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula wherein R ⁇ is Cj ⁇ "Ci8 hydrocarbyl and mixtures thereof, preferably ⁇ Q, C ⁇ 2, ⁇ 4 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • R* is derived from (coconut) C12-C14 alkyl fraction fatty acids, R ⁇ is methyl and ApR ⁇ and A'qR ⁇ are each monoethoxy.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • R ⁇ is Cjo-Cj hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R ⁇ is -C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • An preferred additional components of the components or compositions is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent components or compositions herein.
  • a preferred feature of the components or compositions is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is incorporated directly into the components or compositions.
  • Components or compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • O i i X - C - OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5%) to 20%) by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10%) by weight of the detergent compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching components or compositions.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • Y is H or a solubi zing group. Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO M , -CO2 M , -SO M , -N (R ) .X ⁇ and
  • R 3 is an alkyl chain containing from 1 to 4 carbon atoms
  • M is a cation which provides solubility to the bleach activator
  • X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N ⁇ N ⁇ tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • R ⁇ is an alkyl group with from 1 to 14 carbon atoms
  • R- is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • the detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15%> by weight, more preferably from 1% to 10%> by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R N — R z OOH R N R ⁇ OOH
  • R! is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
  • the components or compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80%) by weight, preferably from 10%> to 60%> by weight, most preferably from 15% to 40%) by weight of the composition.
  • a water-soluble builder compound typically present in detergent compositions at a level of from 1% to 80%) by weight, preferably from 10%> to 60%> by weight, most preferably from 15% to 40%) by weight of the composition.
  • the detergent components or compositions of the invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5%> to 60%>, more preferably from 5% to 50%>, more preferably from 8%> to 40.
  • the phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • the most preferred polycarboxyhc acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1 %> to 15%>, more preferably from 0.5% to 8%> by weight of the composition.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1, 2,3 -propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • the components or compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8%> to 40%> weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10%> to 28%, more preferably from 18%> to 22%> water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
  • Zeolite X has the formula Na [(AlO 2 )86(Si ⁇ 2)l06J- 276 H 2 O.
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1%> to 80%>, more preferably from
  • Zeohte MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A.
  • Heavy metal ion sequestrant The components or compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%>, preferably from 0.1 % to 5%, more preferably from 0.25%> to 7.5%> and most preferably from 0.3%) to 2% by weight of the compositions or component
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1.1 hydroxyethane dimethylene phosphonic acid.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-509,382 The ⁇ -alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide- N,N'-disuccinic acid Glycinamide- N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • diethylenetriamine pentacetic acid ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N,N'- disuccinic acid
  • 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Another preferred ingredient useful in the components or compositions herein is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent components or compositionss. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor Intemational, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001%) to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A S.
  • Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%) to 2%o active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%> to 2%o by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudo onas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred additional components of the components or compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent components or compositionss, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quatemised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1 %> to 15%, most preferably from 0.5%> to 10%> by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent components or compositionss herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
  • Another organic compound which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
  • X is a nonionic group selected from the group consisting of H, C1 -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • the detergent compositions of the invention when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%., preferably from 0.02% to 10%, most preferably from 0.05%o to 3% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cl 8-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • a preferred suds suppressing system comprises:
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
  • silica silicone antifoam compound is incorporated at a level of from 5% to 50%,, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78%) and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1, at a level of from 0.5% ⁇ to 10%, preferably 1% to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Coming under the tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a C ⁇ ⁇ -C i g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of
  • suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxyhc polymers, such as copolymers of laic and acrylic acid.
  • compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05%> to 0.5%) by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • compositions herein also optionally contain from about 0.005%) to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • R ⁇ is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation.
  • Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N- methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • Rj is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
  • SRA polymeric soil release agents
  • compositions typically from 0.1 %> to 5%>, preferably from 0.2%, to 3.0%) by weight, of the compositions.
  • the additional SRP's include hydrophivally modified cellulose derivatives, such as ester derivatives of CMC. Also included are nonionic cellulose ethers and derivatives.
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification oligomerization, often with a metal catalyst such as a titanium(rV) alkoxide.
  • esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG ,2-propylene glycol
  • SRA's include the nonionic end- capped 1 ,2-p ⁇ opylene/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. 4,71 1,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721 ,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the aniomc, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • Gosselink et al 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; Other Optional Ingredients
  • compositionss of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions contain from about 2%> to about 10%> by weight of an organic acid, preferably citric acid.
  • an organic acid preferably citric acid.
  • minor amounts e.g., less than about 20%> by weight
  • neutralizing agents e.g., buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4.285,841 to Barrat et al, issued August 25, 1981 (herein incorporated by reference), can be present.
  • the components or compositions herein can take a variety of physical forms including liquid and solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
  • the components or compositions can be made via a variety of methods, depending on their product form.
  • the solid compositions or components can be made by methods such as dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.
  • the cyclic amine based polymers and the anionic cellulose materials herein are present in an intimate mixture.
  • this mixture can be obtained by any mixing method, including agglomeration.
  • the intimate mixture are preferably in the form of a compacted, agglomerated or spray dried granule.
  • Detergent compositions and components herein preferably have a bulk density of from 300g/litre or even 350g/litre or 450g/litre to preferably 1500g/litre or lOOOg/litre or even to 850g/litre.
  • the present invention also provides a method for laundenng. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent components or compositions herein before descnbed or formed from the individual components of such components or compositions. Contacting of fabncs with washing solution will generally occur under conditions of agitation although the components or compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment. As discussed above, it is preferred that the washing solution have a pH of less than about 1 1.0, preferably it has a pH of less than 10.5 and most preferably it has a pH of less than 9.5.
  • An effective amount of a high density liquid or granular detergent components or compositions in the aqueous wash solution in the washing machine is preferably from about 500 to about 10000 ppm or even 7000 ppm, more preferably from about 1000 to about 3000 ppm.
  • the detergent components or compositions herein may also be used to treat and condition fabncs and textiles.
  • a fabnc conditioning components or compositions comprising the cyclic amine based polymers and anionic cellulose polymers as desc ⁇ bed herein, may be added dunng the nnse cycle of a conventional home laundenng operation in order to impart the desired fabric appearance and mtegnty benefits hereinbefore descnbed.
  • composition or component is one or more fabnc softener actives, such as cationically charged hydrocarbons, such as C12-C22 dialkyl substitued quaternary ammonium salts and/ or clays, optionaly with a flocculating polymer.
  • fabnc softener actives such as cationically charged hydrocarbons, such as C12-C22 dialkyl substitued quaternary ammonium salts and/ or clays, optionaly with a flocculating polymer.
  • composition or component herein may be present in or in the form of a softening and cleaning composition, such as for example descnbed in EP-B1-313146 and W093/ 01267, preferably compnsing additional softening ingredients, such as clay and optionally a flocculating polymer.
  • a softening and cleaning composition such as for example descnbed in EP-B1-313146 and W093/ 01267, preferably compnsing additional softening ingredients, such as clay and optionally a flocculating polymer.
  • Adduct of Imidazole-epichlorohyd ⁇ n-t ⁇ sglycidyl ether from glycerine (Ratio of ⁇ m ⁇ dazole:ep ⁇ chlorohyd ⁇ n: tnsglycidylether 2.0:1.76:0.26)
  • Adduct of piperazine.morpholine and epichlorohydnn (ratio 0.9: 0.4: 1.0)
  • Adduct of piperazine, pipendine and epichlorohydnn (ratio 0.9: 0.4: 1.0)
  • Adduct of imidazole, piperazine and epichlorohydnn (ratio 2: 1 :3)
  • Adduct of imidazole, piperazine and epichlorohydnn (ratio 1 :1:2)
  • Adduct of imidazole, 1 ,6 diammohexane and epichlorohydnn (ratio 1 : 1:2)
  • Adduct of imidazole, dimethylaminopropylamme and epichlorohydnn (ratio 1.02:0.34: 1.0)
  • Adduct of imidazole-epichlorohydnn and 3chlorohydroxypropyl sulfonic acid (ratio: 1.0:0.83:0.34)
  • Adduct of imidazole-epichlorohydnn and 3 chlorohydroxypropyl sulfomc acid (ratio: 1.0:0.75:0.5)
  • Adduct of imidazole, piperazine and epichlorohydnn (Ratio- 1.0: 1.0:2.0) quat with 0.22 moles of chloroacetate
  • Adduct of piperazine, morpholine and epichlorohydnn (ratio 1 :0.2: 1) 100% oxidized
  • Adduct of imidazole, piperazine and epichlorohydnn 100% oxidized
  • LAS Sodium linear Cl 1-13 alkyl benzene sulfonate LAS (I) Potassium linear or branched Cl 1-13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide
  • Nal2(AlO2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • Citric acid I Anhydrous citric acid.
  • Citric acid II Monohydrate citric acid, Malic acid Anhydrous malic acid, 80%> having a particle size of from 50 microns to 100 microns, having a volume median particle size of
  • Maleic acid Anhydrous maleic acid, 80%o having a particle size of from 5 microns to 30 microns, having a volume median particle size of 15 microns Tartaric acid Anhydrous tartaric acid, 80%> having a particle size of from 25 microns to 75 microns, having a volume median particle size of 50 microns
  • MA AA Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000
  • Protease Proteolytic enzyme having 3.3%, by weight of active enzyme, sold by NOVO Industries A S under the tradename Savinase
  • Protease I Proteolytic enzyme, having 4%, by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A S
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
  • Lipase Lipolytic enzyme having 2.0%, by weight of active enzyme, sold by
  • Lipolase Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A S
  • PB4 Particle containing sodium perborate tetrahydrate of nominal formula NaBO2.3H2 O the particles having a weight average particle size of 950 microns, 85%, particles having a particle size of from 850 microns to 950 microns
  • PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202 the particles having a weight average particle size of 800 microns, 85%> particles having a particle size of from 750 microns to 950 microns
  • the particles having a weight average particle size of 850 microns, 5%> or less having a particle size of less than
  • NOBS Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns
  • NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate
  • PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000
  • PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters SRP2 Diethoxylated poly (1 , 2 propylene terephtalate) short block polymer
  • PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1
  • Opacifier Water based monostyrene latex mixture, sold by BASF
  • Effervescence granule any of the effervescence granules I to XII In the following examples all levels are quoted as %> by weight of the composition:
  • compositions are in accordance with the invention.
  • Adduct 1 , 2, 4 or 5 1.0 0.5 2.0
  • Adduct 1 , 2 or 6 0.3 1.0 2.0 0.8 1.0
  • Rapeseed 4.0 2.0 1.0 - 1.0 - 3.5 - fatty acid
  • Adduct 1 0.3 0.4 0.5 1.0 1.0 2.0 0.5 1.0 or 2

Abstract

The present invention relates to detergent compositions or components comprising certain cyclic amine based polymers and certain anionic cellulose materials. This combination imparts improved appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions, whilst also providing improved whiteness and/or brightness maintenance.

Description

DETERGENT COMPOSITIONS OR COMPONENTS
TECHNICAL FIELD
The present invention relates to compositions or components composing certain cyclic amme based polymers and certain anionic cellulose mateπals
BACKGROUND OF THE INVENTION
It is known that fabrics and textiles simply wear out over time and with use. Also, the laundeπng of the fabrics and textiles, over many cycles, can accentuate and contnbute to the detenoration of the integrity and the appearance of such fabncs and textiles. Detenoration of fabric mtegnty and appearance can manifest itself in several ways For example, short fibers are dislodged from and knit fabric/textile structures by the mechanical action of laundeπng These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabncs and dimmish the appearance of newness of the fabnc Further, repeated laundenng of fabncs and textiles, especially ith bleach-containing laundry products, can remove dye from fabncs and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color
Given the foregoing, there is clearly an ongoing need to identify mateπals which could be added to laundry detergent products that would associate themselves with the fibers of the fabncs and textiles laundered using such detergent products and thereby reduce or minimize the tendency of the laundered fabnc/textiles to deteπorate in appearance Any such detergent product additive mateπal should, of course, be able to benefit fabric appearance and mtegnty without unduly interfeπng with the ability of the laundry detergent to perform its fabric cleaning function. Co- pendmg applications PCTΛJS98/19143 describes the use of certain cyclic amme based polymers which are found to provide excellent mtegnty benefits to fabncs
Die inventor has now found that when these amine based polymers are used in combination with specific anionic cellulose matenal, the fabnc care and fabnc integrity can be further improved. It is believed that these benefits are achieved because the anionic cellulose mateπal and the amme based polymers having a positively charged group, interact together in such a manner that both polymenc mateπals have an improved surface activity, resulting in a better interaction with or deposition onto the surface of the fabnc. It is believed that when the polymeπc mateπals are present in an intimate mixture, such an interaction between the polymeπc mateπals is even more likely to occur or even stronger, resulting in a greater benefit obtained when the polymeπc matenals are present in the product as an intimate mixture or in the same component or granule.
Not only an improved fabnc integrity is achieved, but also an improved soil removal and whiteness or bnghtness maintenance is achieved when these compounds are used together. The inventor also found that when the anionic cellulose matenal and the amme based polymer are present in an intimate mixture, such as in the form of an agglomerate, a compacted granule or a spray dried granule, these benefits are even more apparent.
SUMMARY OF THE INVENTION
The present invention relates to a detergent composition or component or additive compnsing: a) from 0.01% to 90% by weight, preferably from 0.05% to 50% by weight, of a salt of an anionic cellulose matenal compnsing an anionic substituent group
R - X - Z wherein R is a saturated , unsaturated or aromatic hydrocarbon spacer group, X is oxygen, nitrogen or sulphur, Z is carboxylate, sulphonate, sulphate or phosphonate group: and b) from 0.01% to 90% by weight, preferably from about 0.05% to about 20% by weight of a cyclic amme based polymer.
The present invention also relates to the laundeπng or treating of fabncs and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions or components descnbed herein, or formed from the individual polymenc mateπals of such compositions or components. Laundeπng of fabncs and textiles in such washing solutions imparts fabric appearance benefits to the fabnc and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifadmg, improved abrasion resistance, and/or enhanced softness and also improved whiteness and/ or bnghtness maintenance or even improved cleaning performance The cyclic amine based polymers and the cellulose matenal are preferably in an intimate mixture with one another. In one preferred embodiment, the compounds are intimately mixed pnor to introduction to the composition or component of the invention.
Preferably, the mixture is present in an agglomerated, compacted or spray-dπed particle, when the composition or component is solid.
Hereby it may be preferred that the compounds are mixed with an anionic surfactant, preferably LAS. as described herein after. It may also be preferred that a hydrotrope is admixed to this mixture, preferably STS Also preferably present in the mixture are inorganic and/or organic salts and acids and or silicates or alummosihcates, including zeolite, amorphous silicates, crystalline layered silicates, carbonate, bicarbonate, phosphate, citnc acid, malic acid, maleic acid, tartaπc acid or salts thereof, or mixtures of these ingredients
DETAILED DESCRIPTION OF THE INVENTION
Cyclic amme Based Polymer Mateπals
An essential component, the compositions or components of the present invention compπse one or more cyclic amine based polymer.
When used herein, 'polymers' include not only polymers, but also ohgomers, co-polymers, co- ohgomers, present in any structural arrangement, also including cross-linked arrangements. As will be apparent to those skilled in the art, an ohgomer is a molecule consisting of only a few monomer units while polymers compπse considerably more monomer units. For the present invention, ohgomers are defined as molecules having an average molecular weight below about 1 ,000 and polymers are molecules having an average molecular weight of greater than about 1 ,000, copolymers or co-oligomers are mateπals wherein two or more dissimilar monomers have been simultaneously or sequentially polymenzed. Copolymers or co-oligomers of the present invention can include, for example, polymers or ohgomers polymenzed from a mixture of a primary cyclic amme based monomer, e.g., piperadine, and a secondary cyclic amme monomer, e.g., morphohne.
Depending on the application of the composition or component herein, the amount of cyclic amine based polymer may very. The cyclic amine based polymers herein will generally be about 0.01% to about 90% by the weight of the detergent composition or component, more preferably from 0.05% to 20% or even from 0.05% to 15% by weight. In detergent compositions herein it may for example be preferred that the polymer is present at a level of from 0.05% to 10% by weight of the detergent composition, preferably from 0.05% to 5% or even from 0.05% to 3% or even 0 1% to 2% by weight. In detergent components or additives, the polymer may preferably be present at a level of 0.05% to 40% by weight or even from 0.05% to 20% or even 0.1% to 15% or even 1 % to 10% by weight.
The cyclic amine based polymer herein is preferably present in the composition or component m such an amount that the concentration of cyclic amme m the wash is from 100 ppm to 10,000 ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm
The preferred cyclic amine based polymers herein can be charactenzed by the following general formula
Figure imgf000006_0001
wherein. each T is independently selected from the group consisting of H, Cι -Cι 2 alkyl, substituted alkyl,
C7-C12 alkylaryl,
-(CH2)hCOOM, -(CH2)hSO3M. CH2CH(OH)SO3M, -(CH2)hOSO3M,
Figure imgf000006_0002
Figure imgf000006_0003
-wherein W compnses at least one cyclic constituent selected from the group consisting of:
Figure imgf000007_0001
in addition to the at least one cyclic constituent, W may also compπse an aliphatic or substituted aliphatic moiety of the general structure,
Figure imgf000007_0002
-each B is independently CJ-CJ alkylene. Cι -Cι2 substituted alkylene, C3-Cι 2 alkenylene, Cg- Cj2 dialkylarylene. Cg-Cj dialkylarylenediyl, and -(R5θ)nR5- ;
-each D is independently C2-Cg alkylene;
-each Q is independently selected from the group consisting of hydroxy, Ci -Cig alkoxy, C -Cι g hydroxyalkoxy, ammo, Cj-Ci alkylammo, dialkylamino, tπalkylamino groups, heterocyclic monoamino groups and diamino groups;
-each Rj is independently selected from the group consisting of H, Ci-Cg alkyl and Cj-Cg hydroxyalkyl;
-each R2 is independently selected from the group consisting of C] -Cι 2 alkylene, CJ -CJ2 alkenylene, -CH2-CH(ORι )-CH2, Cg-Cj2 alkarylene, C4- 2 dihydroxyalkylene, poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH2OR2OCH2CH(OH)CH2-, and C3- C\2 hydrocarbyl moieties; provided that when R2 is a C3-Cι2 hydrocarbyl moiety the hydrocarbyl moiety can compnse from about 2 to about 4 branching moieties of the general structure: OH
-{-OR.5 ^ O— CH2-CH-CH2 "J- w— R2 2I-W-T ^ x -each R3 is independently selected from the group consisting of H, O, R2, C]A20 hydroxyalkyl, Cj-C2o alkyl, substituted alkyl, Cg-Cj \ aryl, substituted aryl, C7-C1 1 alkylaryl, C I -C2Q ammoalkyl, -(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
Figure imgf000008_0001
-each R4 is independently selected from the group consisting of H, Cj-C 2 alkyl, Cj-C hydroxyalkyl, aryl and C -C22 alkylaryl; -each R5 is independently selected from the group consisting of C2-Cg alkylene, C -Cg alkyl substituted alkylene; and
A is a compatible monovalent or di or polyvalent anion;
M is a compatible cation; b = number necessary to balance the charge; each x is independently from 3 to about 1000; each c is independently 0 or 1 ; each h is independently from about 1 to about 8; each q is independently from 0 to about 6; each n is independently from 1 to about 20; each r is independently from 0 to about 20; and each t is independently from 0 to 1.
The cyclic amme based polymer may compπse combinations of these cyclic amine based materials. For example, a mixture of piperadine and epihalohydrin condensates can be combined with a mixture of morpholine and epihalohydrin condensates to achieve the desired fabric treatment results. Moreover, the molecular weight of cyclic polymers can vary within the mixture as is illustrated herein.
Preferred compounds that fall within this general structure include compounds: - wherein each R\ is H; and -at least one W is selected from the group consisting of:
Figure imgf000009_0001
Even more preferred compounds are those:
-wherein each R] is H: and
-at least one W is selected from the group consisting of:
Figure imgf000009_0002
And most preferred compounds are those:
-wherein each R\ is H; and
-at least one W is selected from the group consisting of:
Figure imgf000010_0001
Preferred compounds to be used as the linking group R2 include, but are not limited to. polyepoxides, ethylenecarbonate, propylenecarbonate, urea, α, β-unsaturated carboxylic acids, esters of α, β-unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids, anhydrides of α, β-unsaturated carboxylic acids, di- or polycarboxyhc acids, esters of di- or polycarboxyhc acids, amides of di- or polycarboxyhc acids, anhydπdes of di- or polycarboxyhc acids, glycidylhalogens, chloroformic esters, chloroacetic esters, denvatives of chloroformic esters, denvatives of chloroacetic esters, epihalohydnns, glycerol dichlorohydπns, bis- (halohydπns), polyetherdihalo-compounds, phosgene, polyhalogens, functionalized glycidyl ethers and mixtures thereof. Moreover, R2 can also compnse a reaction product formed by reacting one or more of polyetherdiamines, alkylenediammes. polyalkylenepolyammes, alcohols, alkyleneglycols and polyalkyleneglycols with α, β-unsaturated carboxylic acids, esters of α, β- unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids and anhydrides of α, β- unsaturated carboxylic acids provided that the reaction products contain at least two double bonds, two carboxylic groups, two amide groups or two ester groups.
Also preferred cyclic amme based polymers for use herein include adducts of two or more compositions selected from the group consisting of piperazme, piperadine. epichlorohydnn, epichlorohydnn benzyl quat, epichlorohydnn methyl quat, morphohne and mixtures thereof.
Highly preferred cyclic amme based polymers herein are referred to as Imidazole-epi chlorohydπn copolymers.
These cyclic amine based polymers can be linear or branched. One specific type of branching can be introduced using a polyfunctional crosslinking agent. An example of such such polymer is exemplified below.
Figure imgf000011_0001
Anionic cellulose mateπal
The compositions or components herein compπse a salt of an anionic cellulose mateπal comprising an anionic substituent group R - X - Z wherem R is a saturated , unsaturated or aromatic hydrocarbon spacer group, X is oxygen, nitrogen or sulphur, Z is carboxylate, sulphonate, sulphate or phosphonate group.
The hydrocarbon spacer group is preferably a C|-C|8, more preferably a C C|4, or even more preferably a C C saturated , unsaturated or aromatic group, preferably an alkylene group. T e spacer group may also be substituted with one or more hydroxy groups.
The group X is preferably a nitrogen, or even more preferably an oxygen atom.
The group Z is preferably a carboxylate group.
Highly preferred hereon are the so-called salts of carboxyalkyl celluloses, whereby preferably the alkylene group (or the so-called alkyl group) compnses from 1 to 4 carbon atoms. Most preferred herein is a salt of carboxymethyl cellulose.
The cation of the salt is preferably a potassium ion or more preferably a sodium ion.
Depending on the application of the composition or component herein, the amount of cellulose material may very. The anionic cellulose mateπal herein will generally be about 0.01% to about 90% by the weight of the detergent composition or component, more preferably from 0.05% to 50% or even from 0.05% to 20%. In detergent compositions herein it may for example be preferred that the mateπal is present at a level of from 0.05% to 10% by weight of the detergent composition, preferably from 0.05% to 7% or even from 0.05% to 5% or even 0.5% to 3%. In components herein, such as detergent additives, the matenal may preferably be present at a level of 0.05% to 40% by weight of the component, or even from 0.05% to 20% or even 0.1% to 15% or even l% to 10%.
The anionic cellulose material herein is preferably present in the composition or component in such an amount that the concentration of cyclic amme in the wash is from 100 ppm to 10,000 ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm.
Detergent compositions or components
The compositions or components of the invention are preferably laundry, compositions, preferably in the form of granules, extrudates, flakes or tablets, liquids or pastes.
The compositions or components in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
They preferably contain one or more additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, additional organic polymeric compounds, including dispersants, soil suspension and anti-redeposition agents soil releasing agents, enzymes, suds suppressors, lime soap, , perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
Preferred additional ingredients are hydrophobically modified ether and ester cellulosic polymers as descnbed in co-pending application PCT US98/19139 and PCT/US98/19142. These polymers may be present at a level of from 0.01% to 10% by weight of the composition, more preferably at a level of from 0.05% to 5% by weight or even form 0.1 % to 2% by weight of the composition, or at a level of from 0.05% to 30% by weight of the component, more preferably at a level of from 0.1 % to 20% by weight or even form 0.3%) to 10%o by weight of the component. Also highly preferred are enzymes, cationic softening agents, clay, optionally together with polymeric flocculants, dye transfer inhibitors, or preferably mixtures thereof, as described herein after.
Surfactant
The components or compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
Anionic Surfactant
The components or compositions in accord with the present invention preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent components or compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, --C, monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C---C, . diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary C J O-C I g alkyl sulfates, more preferably the C\ \-C\ 5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 1- Ci 8, most preferably C\ 1- 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfonate Surfactant Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxyhc acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic Carboxylate Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)x CH2C00"M+ wherein R is a to Cj g alkyl group, x ranges from O to 10, and the ethoxvlate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRι-CHR2-O)-R3 wherein R is a C to C1 g alkyl group, x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l -undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressers.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
(RJ ) CH2 COOM, wherein R is a C5-Cj 7 linear or branched alkyl or alkenyl group, R^ is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
Nonionic Alkoxylated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic Polvhvdroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^CONR^Z wherein : Rl is H, -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C\ 1-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Fatty Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula: R6C0N(R )2 wherein R is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R' is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)xH, where x is in the range of from 1 to 3.
Nonionic Alkylpolvsaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R2θ(CnH2nO)t(glycosyl)x
wherein R- is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R^(OR^)xN^(R^)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Cjo-Ci g alkyl dimethylamine oxide, and C J Q-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent components or compositionss in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2COO~ wherein R is a Cg-Ci g hydrocarbyl group, each R* is typically C1-C3 alkyl, and R^ is a C1-C5 hydrocarbyl group. Preferred betaines are C\ 2-18 dimethyl-ammonio hexanoate and the 10- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Cationic Surfactants Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono Cg- C\β, preferably Cβ-Cio N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:
Figure imgf000020_0001
wherein \ is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R^ and R^ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R^ and R are methyl groups; R^ is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR'* group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR^ groups are — CH2CH2OH, — CH2CH2CH2OH, — CH2CH(CH3)OH and — CH(CH3)CH2OH, with— CH2CH2OH being particularly preferred. Preferred R1 groups are linear alkyl groups. Linear Rl groups having from 8 to 14 carbon atoms are preferred.
Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
C
Figure imgf000020_0002
wherein R! is Cjø-Ci hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C 10 and Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide. As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and or Pr and/or i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2%) to 7%, most preferably from 0.3%> to 3.0% by weight of the composition.
Cationic bis-alkoxylated amine surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general formula II:
Figure imgf000021_0001
wherein R! is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R^ is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R^ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula
Figure imgf000022_0001
wherein R^ is Cjθ"Ci8 hydrocarbyl and mixtures thereof, preferably \Q, C\2, \4 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R* is derived from (coconut) C12-C14 alkyl fraction fatty acids, R^ is methyl and ApR^ and A'qR^ are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
Figure imgf000022_0002
wherein R^ is Cjo-Cj hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R^ is -C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
Perhydrate Bleaches
An preferred additional components of the components or compositions is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2Cθ3-3H2θ2, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent components or compositions herein.
Organic Peroxyacid Bleaching System
A preferred feature of the components or compositions is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the components or compositions. Components or compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
O
X- C - L
where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
O i i X - C - OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5%) to 20%) by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10%) by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Leaving Groups
The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching components or compositions.
Preferred L groups are selected from the group consisting of:
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000025_0002
R3 0 Y
1 " '
-0-C=CHR4 , and — N— S-CH— R4
R3 O
and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to
14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubi zing group. Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -SO M , -CO2 M , -SO M , -N (R ) .X~ and
O<— N(R 3 ), and most preferably -SO., - M + and -CO7 - M + wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably,
M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis. Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N^N^ tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R1 - — c- - N — - P2 -c — N - R 2_r_,
0 R5 0 or R5 O O
wherein R^ is an alkyl group with from 1 to 14 carbon atoms, R- is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Preformed Organic Peroxyacid
The detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15%> by weight, more preferably from 1% to 10%> by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R N — Rz OOH R N R< OOH
I i I c ' • c ' I "
O Rb O or R5 O 0
wherein R! is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.
Water-Soluble Builder Compound
The components or compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80%) by weight, preferably from 10%> to 60%> by weight, most preferably from 15% to 40%) by weight of the composition.
The detergent components or compositions of the invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5%> to 60%>, more preferably from 5% to 50%>, more preferably from 8%> to 40.
The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l ,l,3-propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxyhc acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1 %> to 15%>, more preferably from 0.5% to 8%> by weight of the composition.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1, 2,3 -propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The components or compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8%> to 40%> weight of the composition.
Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10%> to 28%, more preferably from 18%> to 22%> water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
Na i2 [Alθ2) i2 (Siθ2)i2J. H2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na [(AlO2)86(Siθ2)l06J- 276 H2O.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1%> to 80%>, more preferably from
15%o to 40%) by weight of the compositions.
Zeohte MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
The d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A.
Heavy metal ion sequestrant The components or compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%>, preferably from 0.1 % to 5%, more preferably from 0.25%> to 7.5%> and most preferably from 0.3%) to 2% by weight of the compositions or component
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1.1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. Glycinamide- N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Enzyme
Another preferred ingredient useful in the components or compositions herein is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent components or compositionss. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor Intemational, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001%) to 4% active enzyme by weight of the composition. Preferred amylases include, for example, -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%) to 2%o active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%> to 2%o by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudo onas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the components or compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent components or compositionss, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quatemised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1 %> to 15%, most preferably from 0.5%> to 10%> by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A- 1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent components or compositionss herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
Another organic compound, which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
Figure imgf000035_0001
wherein X is a nonionic group selected from the group consisting of H, C1 -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.
Suds Suppressing System
The detergent compositions of the invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%., preferably from 0.02% to 10%, most preferably from 0.05%o to 3% by weight of the composition. Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cl 8-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50%> to 99%>, preferably 75% to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silica silicone antifoam compound is incorporated at a level of from 5% to 50%,, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78%) and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1, at a level of from 0.5%ι to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Coming under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C \ β-C i g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of
Figure imgf000038_0001
Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxyhc polymers, such as copolymers of laic and acrylic acid.
Polymeric Dye Transfer Inhibiting Agents
The compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05%> to 0.5%) by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
Optical Brightener
The compositions herein also optionally contain from about 0.005%) to 5% by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the structural formula:
Figure imgf000038_0002
wherein R\ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R\ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N- methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, Rj is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-mo hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
Polymeric Soil Release Agent
Additional polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01%ι to
10.0%), typically from 0.1 %> to 5%>, preferably from 0.2%, to 3.0%) by weight, of the compositions.
The additional SRP's include hydrophivally modified cellulose derivatives, such as ester derivatives of CMC. Also included are nonionic cellulose ethers and derivatives. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification oligomerization, often with a metal catalyst such as a titanium(rV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1 ,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end- capped 1 ,2-pτopylene/polyoxyethylene terephthalate polyesters of U.S. 4,71 1,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721 ,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the aniomc, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; Other Optional Ingredients
Other optional ingredients suitable for inclusion in the components or compositionss of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
Highly preferred compositions contain from about 2%> to about 10%> by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20%> by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4.285,841 to Barrat et al, issued August 25, 1981 (herein incorporated by reference), can be present.
Form of the Components or compositionss
The components or compositions herein can take a variety of physical forms including liquid and solid forms such as tablet, flake, pastille and bar, and preferably granular forms. The components or compositions can be made via a variety of methods, depending on their product form. The solid compositions or components can be made by methods such as dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.
It is highly preferred that the cyclic amine based polymers and the anionic cellulose materials herein are present in an intimate mixture. In solid compositins hor components herein, this mixture can be obtained by any mixing method, including agglomeration. The intimate mixture are preferably in the form of a compacted, agglomerated or spray dried granule.
Detergent compositions and components herein preferably have a bulk density of from 300g/litre or even 350g/litre or 450g/litre to preferably 1500g/litre or lOOOg/litre or even to 850g/litre. Fabnc Laundenng Method
The present invention also provides a method for laundenng. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent components or compositions herein before descnbed or formed from the individual components of such components or compositions. Contacting of fabncs with washing solution will generally occur under conditions of agitation although the components or compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment. As discussed above, it is preferred that the washing solution have a pH of less than about 1 1.0, preferably it has a pH of less than 10.5 and most preferably it has a pH of less than 9.5.
An effective amount of a high density liquid or granular detergent components or compositions in the aqueous wash solution in the washing machine is preferably from about 500 to about 10000 ppm or even 7000 ppm, more preferably from about 1000 to about 3000 ppm.
Fabric Conditioning and Softening
The detergent components or compositions herein may also be used to treat and condition fabncs and textiles. Thus, for example, a fabnc conditioning components or compositions comprising the cyclic amine based polymers and anionic cellulose polymers as descπbed herein, may be added dunng the nnse cycle of a conventional home laundenng operation in order to impart the desired fabric appearance and mtegnty benefits hereinbefore descnbed. Then, preferably at least about 1%, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to about 60% by weight, of the composition or component is one or more fabnc softener actives, such as cationically charged hydrocarbons, such as C12-C22 dialkyl substitued quaternary ammonium salts and/ or clays, optionaly with a flocculating polymer.
Alternatively, the composition or component herein may be present in or in the form of a softening and cleaning composition, such as for example descnbed in EP-B1-313146 and W093/ 01267, preferably compnsing additional softening ingredients, such as clay and optionally a flocculating polymer.
The following are chemical structures for certain cyclic amine based polymers herein, prepared as descnbed in co-pending applications PCT US98/19143 and PCT/US98/19142. Side reactions expected to occur dunng the condensation are not shown. Table 1
Example Matenal
Adduct of Imidazole-epichlorohydnn
(Ratio of ιmιdazole:epιchlorohydnn 1 : 1, Polymer from Example
1)
(Idealized Structure)
Adduct of Imidazole-epichlorohydnn
(Ratio of ιmιdazole:epιchlorohydnn 1.36: 1 , Polymer from
Example 2)
OH
(Idealized Structure)
Adduct of Imidazole-epichlorohydnn (Ratio of ιmιdazole:epιchlorohydπn 1.75:1)
Figure imgf000044_0001
(Idealized Structure)
Adduct of Imidazole-epichlorohydπn-tπsglycidyl ether from glycerine (Ratio of ιmιdazole:epιchlorohydπn: tnsglycidylether 2.0:1.76:0.26)
Figure imgf000044_0002
Idealized Structure Adduct of Imidazole-epichlorohydnn- -tnsglycidyl ether from glycenne(Ratιo of ιmιdazole:epιchlorohydnn: -tnsglycidyl ether from glycenne 2.0: 1.9:0.1 )
Figure imgf000045_0001
Adduct of piperazine and epichlorohydnn (ratio 1:1)
OH
\_y
Adduct of piperazine and epichlorohydnn (ratio 1 : 1), benzyl quat
OH
Adduct of piperazine and epichlorohydnn (ratio 1 : 1) methyl quat
Figure imgf000045_0002
Adduct of piperazine.morpholine and epichlorohydnn (ratio 0.9: 0.4: 1.0)
Figure imgf000045_0003
Adduct of piperazine, pipendine and epichlorohydnn (ratio 0.9: 0.4: 1.0)
Figure imgf000045_0004
Adduct of piperazine, morpholine and epichlorohydnn (ratio 0.9: 0.4: 1.0) methyl quat
Figure imgf000046_0001
Adduct of piperazine, pipendme and epichlorohydnn (ratio 0.9: 0.4: 1.0) methyl quat
Figure imgf000046_0002
Adduct of pιperazme,morpholιne and epichlorohydnn (ratio 0.9: 0.4: 1.0) benzyl quat
Figure imgf000046_0003
Adduct of piperazine, pipendine and epichlorohydnn (ratio 0.9: 0.4: 1.0) benzyl quat
Figure imgf000046_0004
Adduct of imidazole, piperazine and epichlorohydnn (ratio 2: 1 :3)
Figure imgf000046_0005
Adduct of imidazole, piperazine and epichlorohydnn (ratio 1 :1:2)
Figure imgf000046_0006
Adduct of imidazole, 1 ,6 diammohexane and epichlorohydnn (ratio 1 : 1:2)
Figure imgf000047_0001
Adduct of imidazole, dimethylaminopropylamme and epichlorohydnn (ratio 1.02:0.34: 1.0)
Figure imgf000047_0002
Adduct of imidazole-epichlorohydnn and chloroacetic acid (Ratio- 1.36:0.97:0.07)
Figure imgf000047_0003
Adduct of imidazole-epichlorohydnn and chloroacetic acid (Ratio- 1.36:0.93:0.14)
Figure imgf000047_0004
Adduct of imidazole-epichlorohydnn and chloroacetic acid (Ratio- 1.36:0.83:0.34)
Figure imgf000047_0005
Adduct of imidazole-epichlorohydnn and 3chlorohydroxypropyl sulfonic acid (ratio: 1.0:0.83:0.34) Adduct of imidazole-epichlorohydnn and 3 chlorohydroxypropyl sulfomc acid (ratio: 1.0:0.75:0.5)
Figure imgf000048_0001
Adduct of imidazole, piperazine and epichlorohydnn (Ratio- 1.0: 1.0:2.0) quat with 0.22 moles of chloroacetate
Figure imgf000048_0002
Adduct of imidazole, piperazine and epichlorohydnn (Ratio- 1.0:3.0:4.0) quat with 0.32 moles of chloroacetate
Figure imgf000048_0003
Adduct of imidazole, piperazine andepichlorohydπn (Ratio- 1.0: 1.0:2.0) quat with 0.45 moles of chloroacetate
Figure imgf000048_0004
Adduct of imidazole and epichlorohdnn, (ratio 1.75: 1 ) oxidized r
O H
Adduct of piperazine and epichlorohydnn (ratio 1:1) 100% oxidized
Figure imgf000048_0005
Adduct of piperazine and epichlorohydnn (ratio 1:1) 50% oxidized
Figure imgf000048_0006
Adduct of piperazine, morpholine and epichlorohydnn (ratio 1 :0.2: 1) 100% oxidized
Figure imgf000049_0001
Adduct of piperazine, morpholine and epichlorohydnn (ratio 1 :0.2: 1)25% methyl quat and oxidized
Figure imgf000049_0002
Adduct of imidazole, piperazine and epichlorohydnn (ratio 1 :3;4) 100% oxidized
Figure imgf000049_0003
Adduct of imidazole, piperazine and epichlorohydnn (ration 1:3:4) 50% oxidized
Figure imgf000049_0004
Adduct of imidazole. piperazine and epichlorohydnn (ration 1 : 1 :2) 100% oxidized
Figure imgf000049_0005
Adduct of imidazole, piperazine and epichlorohydnn (ration 1 :5:6) 100% oxidized
Figure imgf000049_0006
Adduct of imidazole, piperazine and epichlorohydnn (ration 1: 10:11) 100% oxidized
Figure imgf000050_0001
Abbreviations used in the effervescence component and detergent composition examples
LAS Sodium linear Cl 1-13 alkyl benzene sulfonate LAS (I) Potassium linear or branched Cl 1-13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide
CxyEz Clx-Cly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide
QAS R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14 QAS 1 R2.N+(CH3)2(C2H4OH) with R2 = C8 - C 11 APA C8 - CIO amido propyl dimethyl amine Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids
Adduct x Adduct with number x according to table I
STS Sodium toluene sulphonate
CFAA C12-C14 (coco) alkyl N-methyl glucamide
TFAA C16-C18 alkyl N-methyl glucamide
TP FA C12-C14 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate
TSPP Tetrasodium pyrophosphate
Zeolite A Hydrated sodium aluminosilicate of formula
Nal2(AlO2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
NaSKS-6 Crystalline layered silicate of formula d- Na2Si2O5 Citric acid I Anhydrous citric acid. Citric acid II Monohydrate citric acid, Malic acid Anhydrous malic acid, 80%> having a particle size of from 50 microns to 100 microns, having a volume median particle size of
75 microns
Maleic acid Anhydrous maleic acid, 80%o having a particle size of from 5 microns to 30 microns, having a volume median particle size of 15 microns Tartaric acid Anhydrous tartaric acid, 80%> having a particle size of from 25 microns to 75 microns, having a volume median particle size of 50 microns
Carbonate Anydrous sodium carbonate
Bicarbonate Anhydrous sodium bicarbonate
Silicate Amorphous sodium silicate (SiO2:Na2O = 2.0:1)
Sulfate Anhydrous sodium sulfate
Mg sulfate Anhydrous magnesium sulfate
Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850μm
MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000
MA AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000
AA Sodium polyacrylate polymer of average molecular weight 4,500
CMC Sodium carboxymethyl cellulose
Cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals
Protease Proteolytic enzyme, having 3.3%, by weight of active enzyme, sold by NOVO Industries A S under the tradename Savinase
Protease I Proteolytic enzyme, having 4%, by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A S
Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A S under the tradename Carezyme
Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
Lipase Lipolytic enzyme, having 2.0%, by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A S under the tradename Lipolase Ultra
Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A S
PB4 Particle containing sodium perborate tetrahydrate of nominal formula NaBO2.3H2 O, the particles having a weight average particle size of 950 microns, 85%, particles having a particle size of from 850 microns to 950 microns
PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202, the particles having a weight average particle size of 800 microns, 85%> particles having a particle size of from 750 microns to 950 microns
Percarbonate Particle containing sodium percarbonate of nominal formula
2Na2CO3.3H2O2, the particles having a weight average particle size of 850 microns, 5%> or less having a particle size of less than
600 microns and 2%. or less having a particle size of more than
1 180 microns
NOBS Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns
NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns
TAED Particle containing tetraacetylethylenediamine, DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename Dequest 2060
Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer
Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate
EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
HEDP 1,1 -hydroxyethane diphosphonic acid
PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
PEO Polyethylene oxide, with an average molecular weight of 50,000
TEPAE Tetraethylenepentaamine ethoxylate
PVI Polyvinyl imidosole, with an average molecular weight of 20,000
PVP Polyvinylpyrolidone polymer, with an average molecular weight of
60,000
PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000
PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000
QEA bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H 12-N+-(CH3) bis((C2H5O)-(C2H4 O))n, wherein n = from 20 to 30
SRP 1 Anionically end capped poly esters SRP2 Diethoxylated poly (1 , 2 propylene terephtalate) short block polymer
PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
Silicone antifoam : Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1
Opacifier Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron 621
Wax Paraffin wax
Effervescence granule: any of the effervescence granules I to XII In the following examples all levels are quoted as %> by weight of the composition:
TABLE II
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
TABLE HI
The following compositions are in accordance with the invention.
Figure imgf000057_0002
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Table IV
The following are high density and bleach-containing detergent formulations according to the present invention:
Figure imgf000060_0002
Figure imgf000061_0001
Figure imgf000062_0001
Table V
The following liquid composition is in accord with the invention
Component Wt. % Wt. % Wt. %
Cj2-i 5 alkyl ether (2.5) sulfate 38 38 38 \2 glucose amide 6.86 6.86 6.86
Citnc Acid 4.75 4.75 4.75
Cj2-14 Fatty Acid 2.00 2.00 2.00
Enzymes 1.02 1.02 1.02
MEA 1.0 1.0 1.0
Propanediol 0.36 0.36 0.36
Borax 6.58 6.58 6.58
Dispersant 1.48 1.48 1.48
Na Toluene Sulfonate 6.25 6.25 6.25
Adduct 1 , 2, 4 or 5 1.0 0.5 2.0
CMC 1.0 2.5 0.5
Dye, Perfume, Bnghteners, Preservatives, Balance Balance Balance Suds Suppressor, Other Minors, Water
100% 100% 100% Table VI
The following liquid detergent formulations are prepared according to the present invention
A B C D
LAS 1 1.5 9.0 - 4.0
C25E2.5S - 3.0 18.0 - 16.0
C45E2.25S 1 1.5 3.0 - 16.0
C23E9 - 3.0 2.0 2.0 1.0
C23E7 3.2 - - -
CFAA - - 5.0 - 3.0
TPKFA 2.0 - 2.0 0.5 2.0
Citric (50%) 6.5 1.0 2.5 4.0 2.5
Ca formate 0.1 0.06 0.1 -
Na formate 0.5 0.06 0.1 0.05 0.05
STS 4.0 1.0 3.0 1.2
Borate 0.6 - 3.0 2.0 3.0
Na hydroxide 6.0 2.0 3.5 4.0 3.0
Ethanol 2.0 1.0 4.0 4.0 3.0
1.2 Propanediol 3.0 2.0 8.0 8.0 5.0
Monoethanolamine 3.0 1.5 1.0 2.5 1.0
CMC 2.0 1.0 1.0 3.0 0.4
Adduct 1 , 2 or 6 0.3 1.0 2.0 0.8 1.0
Protease 0.03 0.01 0.03 0.02 0.02
Lipase - - 0.002 -
Amylase - - - 0.00
2
Cellulase - - 0.000 0.00 0.0001
2 05
SRP 0.2 - 0.1 -
DTPA - - 0.3 -
PVNO - - 0.3 - 0.2
Brightener 1 0.2 0.07 0.1 -
Silicone antifoam 0.04 0.02 0.1 0.1 0.1 Miscellaneous and water Table VII
The following liquid detergent formulations are according to the present invention
A B C D E F G H
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0
C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFAA - - - 4.5 - 6.0 8.0 8.0
APA - 1.4 - - 3.0 1.0 2.0 -
TPKFA 2.0 - 13.0 7.0 - 15.0 1 1.0 1 1.0
Citnc 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl 12.0 10.0 - - 15.0 - - -
/ tetradeceny
1 succinic acid
Rapeseed 4.0 2.0 1.0 - 1.0 - 3.5 - fatty acid
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0
Propanedio
] 1
Monoethan - - - 5.0 - - 9.0 9.0 olamme
Tπethanola - - 8.0 - - - 0.4 0.3
CMC 0.2 2.0 0.5 0 7 2.0 1.2 1.0 4.0
Adduct 1 0.3 0.4 0.5 1.0 1.0 2.0 0.5 1.0 or 2
DETPMP 1.0 1.0 0.5 1.0 Carbohydra 0.08 0.02 0.01 0.02 se
Protease 0.02 0.02 0.01 .008 - - .003 .003
Lipase - .002 - .002 .004 0.01 0.01 0.01
Amylase .004 .004 0.01 .008 - - .004 .003
Cellulase - - - .002 - - 0.2 0.1
SRP 2 0.3 - 0.3 0.1 1.0 1.5 2.5 2.5
Boric acid 0.1 0.2 1.0 2.0 4.0 4.0 - -
Ca chloride - 0.02 - 0.01 0.1 0.2 0.3 -
Brightener - 0.4 - - 0.4 - - -
1
Suds 0.1 0.3 - 0.1 0.8 0.7 - - suppressor
Opacifier 0.5 0.4 - 0.3 8.0 7.5 8.0 8.2
NaOH up 8.0 8.0 7.6 7.7 to pH Misce aneous and water

Claims

WHAT IS CLAIMED IS:
1. A detergent composition or component comprising: a) from 0.01% to 90% by weight, preferably from 0.05% to 50% by weight, of a salt of an anionic cellulose matenal compnsing an aniomc substituent group
R - X - Z wherein R is a saturated , unsaturated or aromatic hydrocarbon spacer group, X is oxygen, nitrogen or sulphur, Z is carboxylate, sulphonate, sulphate or phosphonate group; and b) from 0.01% to 90% by weight, preferably from about 0.05% to about 20% by weight of a cyclic amine based polymer.
2 A detergent composition or component according to claim 1 wherein the cellulose matenal wherein R is an C,-C alkylene group, X is oxygen.
3 A detergent composition or component according to claim 2 wherem the anionic cellulose material comprises carboxymethyl cellulose, preferably in the form of a sodium salt thereof.
4. A detergent composition or component according to any preceding claim, wherein the cyclic amine based polymers, oligomers or copolymers are of the general formula:
Figure imgf000066_0001
wherein; each T is independently selected from the group consisting of H, Cj-C^ alkyl, substituted alkyl, C7-C12 alkylaryl,
-(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
Figure imgf000066_0002
Figure imgf000067_0001
-wherein W comprises at least one cyclic constituent selected from the group consisting of:
Figure imgf000067_0002
in addition to the at least one cyclic constituent, W may also compnse an aliphatic or substituted aliphatic moiety of the general structure;
Figure imgf000067_0003
-each B is independently Cj-C^ alkylene, Cj-Cι2 substituted alkylene, C3-Cι 2 alkenylene, Cg- C\2 dialkylarylene, Cg-Cj 2 dialkylarylenediyl, and -(R5θ)nR5- ;
-each D is independently C2-C6 alkylene;
-each Q is independently selected from the group consisting of hydroxy, Cj-Ci g alkoxy, C -Cι g hydroxyalkoxy, amino, Cj-Cjg alkylamino, dialkylamino, tnalkylamino groups, heterocyclic monoamino groups and diammo groups;
-each R\ is independently selected from the group consisting of H, Cj-Cg alkyl and Ci-Cg hydroxyalkyl;
-each R2 is independently selected from the group consisting of Cj-Cι alkylene, Cι-Cι2 alkenylene, -CH2-CH(OR!)-CH2, Cg-C12 alkarylene, C4-C12 dihydroxyalkylene, poly(C2-C4 alkyleneoxy)alkylene, H2CH(OH)CH2OR2OCH2CH(OH)CH2-, and C3- Cj2 hydrocarbyl moieties; provided that when R; is a C3-Cj 2 hydrocarbyl moiety the hydrocarbyl moiety can compπse from about 2 to about 4 branching moieties of the general structure: OH -(-OR5 -) -0— CH2-CH— CH3-[W— R^-W-T
-each R3 is independently selected from the group consisting of H, O, R2, C ]_-C hydroxyalkyl, C]-C2o alkyl, substituted alkyl, C6-Cj \ aryl, substituted aryl, C -Cj \ alkylaryl, C] -C2Q ammoalkyl, -(CH2)hCOOM, -(CH2)hSO3M, CH2CH(OH)SO3M, -(CH2)hOSO3M,
COO M -CH COO M COOM
COOM
SCH-COOM CH -CH, ,COOM
/ \ COOM
C H CH2-COO M -CHf ^ and COOM
-each R4 is independently selected from the group consisting of H, Cj-C22 alkyl, Cj-C22 hydroxyalkyl. aryl and Cy-C22 alkylaryl; -each R5 is independently selected from the group consisting of C2-Cg alkylene, C2-Cg alkyl substituted alkylene: and
A is a compatible monovalent or di or polyvalent anion;
M is a compatible cation; b = number necessary to balance the charge; each x is independently from 3 to about 1000; each c is independently 0 or 1 ; each h is independently from about 1 to about 8; each q is independently from 0 to about 6; each n is independently from 1 to about 20; each r is independently from 0 to about 20; and each t is independently from 0 to 1.
5. A detergent composition according to any preceding claim wherein the cyclic amine based polymers are adducts comprising groups selected from the group consisting of piperazine, piperadine, epichlorohydnn, epichlorohydnn benzyl quat, epichlorohydnn methyl quat, morpholine and mixtures thereof, preferably imidazole-epichlorohydnn copolymers.
A detergent composition or component according to claim 4, wherein each R\ is H and at least one W is selected from the group consisting of:
Figure imgf000069_0001
A detergent composition or component according to claim 4, wherein each Rj is H and at least one W is selected from the group consisting of:
Figure imgf000069_0002
A detergent composition or component according to claim 4, wherein each R\ is H and at least one W is selected from the group consisting of:
Figure imgf000070_0001
9. A detergent component or composition according to any preceding claim wherein the cyclic amine based polymer and the anio c cellulose matenal are in an intimate mixture with one another.
10 A component or composition according to claim 9 whereby the intimate mixture is present in or in the form of an agglomerated granule, compacted granule or spray dned granule.
1 1 A laundry composition according to any preceding claim wherein the composition one or more fabric softening components and/ or dye transfer inhibiting components
PCT/US1999/023147 1998-10-13 1999-10-06 Detergent compositions or components WO2000022079A1 (en)

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EP99970415A EP1121409A1 (en) 1998-10-13 1999-10-06 Detergent compositions or components
CA002346292A CA2346292A1 (en) 1998-10-13 1999-10-06 A detergent composition containing a salt of an anionic cellulose material and a cyclic amine based polymer
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
WO2001059054A1 (en) * 2000-02-10 2001-08-16 The Procter & Gamble Company Laundry detergent compositions with a combination of a cyclic amine polymer and a dye transfer inhibitor
WO2001085891A2 (en) * 2000-05-09 2001-11-15 The Procter & Gamble Company Laundry detergent compositions containing a polymer
WO2004024858A1 (en) * 2002-09-12 2004-03-25 The Procter & Gamble Company Polymer systems and cleaning compositions comprising same
WO2004061067A3 (en) * 2002-12-19 2004-12-09 Procter & Gamble Anti-filming materials, compositions and methods
WO2007093817A1 (en) * 2006-02-17 2007-08-23 Reckitt Benckiser N.V. Detergent composition
EP2535401B1 (en) 2011-06-17 2017-01-25 Dalli-Werke GmbH & Co. KG Detergent composition comprising soil-release polymers of improved storage stability

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DE19643281A1 (en) * 1996-10-21 1998-04-23 Basf Ag Use of polycationic condensation products as a color-fixing additive for detergents and laundry aftertreatment agents
WO1999014301A1 (en) * 1997-09-15 1999-03-25 The Procter & Gamble Company Laundry detergent and fabric conditioning compositions with oxidized cyclic amine based polymers

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Publication number Priority date Publication date Assignee Title
US4013787A (en) * 1971-11-29 1977-03-22 Societe Anonyme Dite: L'oreal Piperazine based polymer and hair treating composition containing the same
DE19643281A1 (en) * 1996-10-21 1998-04-23 Basf Ag Use of polycationic condensation products as a color-fixing additive for detergents and laundry aftertreatment agents
WO1999014301A1 (en) * 1997-09-15 1999-03-25 The Procter & Gamble Company Laundry detergent and fabric conditioning compositions with oxidized cyclic amine based polymers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059054A1 (en) * 2000-02-10 2001-08-16 The Procter & Gamble Company Laundry detergent compositions with a combination of a cyclic amine polymer and a dye transfer inhibitor
WO2001085891A2 (en) * 2000-05-09 2001-11-15 The Procter & Gamble Company Laundry detergent compositions containing a polymer
WO2001085891A3 (en) * 2000-05-09 2002-03-28 Procter & Gamble Laundry detergent compositions containing a polymer
US6596678B2 (en) 2000-05-09 2003-07-22 The Procter & Gamble Co. Laundry detergent compositions containing a polymer for fabric appearance improvement
WO2004024858A1 (en) * 2002-09-12 2004-03-25 The Procter & Gamble Company Polymer systems and cleaning compositions comprising same
WO2004061067A3 (en) * 2002-12-19 2004-12-09 Procter & Gamble Anti-filming materials, compositions and methods
US7285171B2 (en) 2002-12-19 2007-10-23 The Procter & Gamble Company Anti-filming materials, compositions and methods
WO2007093817A1 (en) * 2006-02-17 2007-08-23 Reckitt Benckiser N.V. Detergent composition
EP2535401B1 (en) 2011-06-17 2017-01-25 Dalli-Werke GmbH & Co. KG Detergent composition comprising soil-release polymers of improved storage stability

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