[go: up one dir, main page]

EP1116788A1 - Composition de pro-parfum - Google Patents

Composition de pro-parfum Download PDF

Info

Publication number
EP1116788A1
EP1116788A1 EP00870069A EP00870069A EP1116788A1 EP 1116788 A1 EP1116788 A1 EP 1116788A1 EP 00870069 A EP00870069 A EP 00870069A EP 00870069 A EP00870069 A EP 00870069A EP 1116788 A1 EP1116788 A1 EP 1116788A1
Authority
EP
European Patent Office
Prior art keywords
perfume
composition
pro
methyl
acid
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00870069A
Other languages
German (de)
English (en)
Inventor
Johan Smets
Jean Wevers
Rafael Trujillo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP00870069A priority Critical patent/EP1116788A1/fr
Priority to AU2001230894A priority patent/AU2001230894A1/en
Priority to CA002392976A priority patent/CA2392976A1/fr
Priority to EP01903021A priority patent/EP1246899A1/fr
Priority to MXPA02006845A priority patent/MXPA02006845A/es
Priority to PCT/US2001/000822 priority patent/WO2001051599A1/fr
Priority to BR0107549-7A priority patent/BR0107549A/pt
Priority to JP2001551173A priority patent/JP2003519721A/ja
Priority to CN01803500A priority patent/CN1394231A/zh
Priority to US10/168,936 priority patent/US20040018955A1/en
Priority to ARP010100107A priority patent/AR026830A1/es
Publication of EP1116788A1 publication Critical patent/EP1116788A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3734—Cyclic silicones
    • 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
    • C11D3/162—Organic compounds containing Si
    • 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
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation

Definitions

  • the present invention relates to a pro-perfume composition, in particular for use in liquid detergent composition for imparting sustained release of the benefit agent on the treated surfaces like fabrics, in particular dry fabrics.
  • perfumed products are well-known in the art. However, consumer acceptance of such perfumed products like laundry and cleaning products is determined not only by the performance achieved with these products but also by the aesthetics associated therewith. The perfume components are therefore an important aspect of the successful formulation of such commercial products.
  • perfume additives make such compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to surfaces, like fabrics, treated therewith.
  • the amount of perfume carried-over from an aqueous laundry or cleaning bath onto fabrics is often marginal and does not last long on the surface.
  • fragrance materials are often very costly and their inefficient use in laundry and cleaning compositions and ineffective delivery to surfaces like fabrics results in a very high cost to both consumers and laundry and cleaning manufacturers. Industry, therefore, continues to seek with urgency for more efficient and effective fragrance delivery in laundry and cleaning products, especially for improvement in the provision of long-lasting fragrance to the surfaces like fabrics.
  • the present invention is a pro-perfume composition
  • a pro-perfume composition comprising an amino-functional polymer and a benefit agent, characterised in that the pro-perfume composition and the suspending material are in close physical proximity.
  • close physical proximity means one of the following:
  • An essential feature of the invention is a pro-perfume.
  • Pro-perfume compounds for use in the present invention typically comprises an amino-functional component and a benefit agent.
  • amino-functional component examples include those which have chemically reacted with a benefit agent, so-called "amines which form amine reaction products", i.e. a product of reaction between a compound containing a primary amine functional group and/or secondary amine functional group and an active ketone or aldehyde containing component.
  • amines which form amine reaction products i.e. a product of reaction between a compound containing a primary amine functional group and/or secondary amine functional group and an active ketone or aldehyde containing component.
  • Preferred compounds for use herein are polymers which have been previously reacted with an aldehyde and/or ketone perfume ingredient, thereby imparting a more effective scent to the fabrics.
  • one amine compound may carry both primary and secondary amine compound, thereby enabling the reaction with several aldehydes and/or ketones.
  • the primary amine and/or secondary amine compound is also characterized by an Odour Intensity Index of less than that of a 1% solution of methylanthranilate in dipropylene glycol.
  • Odour Intensity Index it meant that the pure chemicals were diluted at 1% in Dipropylene Glycol, odor-free solvent used in perfumery. This percentage is more representative of usage levels.
  • Smelling strips, or so called “blotters” were dipped and presented to the expert panellist for evaluation. Expert panellists are assessors trained for at least six months in odor grading and whose gradings are checked for accuracy and reproducibility versus a reference on an on-going basis. For each amine compound, the panellist was presented two blotters: one reference (Me Anthranilate, unknown from the panellist) and the sample. The panellist was asked to rank both smelling strips on the 0-5 odor intensity scale, 0 being no odor detected, 5 being very strong odor present.
  • Odour Intensity Index of an amine compound suitable for use in the present invention and according to the above procedure.
  • numbers are arithmetic averages among 5 expert panellists and the results are statistically significantly different at 95% confidence level: Methylanthranilate 1% (reference) 3.4 Ethyl-4-aminobenzoate (EAB) 1 % 0.9 1,4-bis-(3-aminopropyl)-piperazine (BNPP) 1% 1.0
  • a general structure for the primary amine compound of the invention is as follows: B-(NH2) n ; wherein B is a carrier material, and n is an index of value of at least 1.
  • Compounds containing a secondary amine group have a structure similar to the above excepted that the compound comprises one or more -NH- groups instead of -NH2. Further, the compound structure may also have one or more of both -NH2 and -NH- groups.
  • Preferred B carriers are inorganic or organic carriers.
  • inorganic carrier carrier which are non-or substantially non carbon based backbones.
  • Preferred primary and/or secondary amines, among the inorganic carriers are those selected from mono or polymers or organic-organosilicon copolymers of amino derivatised organo silane, siloxane, silazane, alumane, aluminum siloxane, or aluminum silicate compounds.
  • Typical examples of such carriers are: organosiloxanes with at least one primary amine moiety like the diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5) 3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll, Academic Press Inc. 1998, London, pp 209, 106).
  • Preferred primary and/or secondary amines are those selected from aminoaryl derivatives, polyamines, amino acids and derivatives thereof, substituted amines and amides, glucamines, dendrimers, polyvinylamines and derivatives thereof, and/or copolymer thereof, alkylene polyamine, polyaminoacid and copolymer thereof, cross-linked polyaminoacids, amino substituted polyvinylalcohol, polyoxyethylene bis amine or bis aminoalkyl, aminoalkyl piperazine and derivatives thereof, bis (amino alkyl) alkyl diamine linear or branched, and mixtures thereof.
  • Preferred aminoaryl derivatives are the amino-benzene derivatives including the alkyl esters of 4-amino benzoate compounds, and more preferably selected from ethyl-4-amino benzoate, phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate, 4-amino-N'-(3-aminopropyl)-benzamide, and mixtures thereof.
  • Preferred polyamines are polyethyleneimines commercially available under the tradename Lupasol like Lupasol FG (MW 800), G20wfv (MW 1300), PR8515 (MW 2000), WF (MW 25000), FC (MW 800), G20 (MW 1300), G35 (MW 1200), G100 (MW 2000), HF (MW 25000), P (MW 750000), PS (MW 750000), SK (MW 2000000), SNA (MW 1000000), most preferably Lupasol HF or WF (MW 25000), P (MW 750000), PS (MW 750000), SK (MW 2000000), SNA (MW 1000000).
  • Preferred amino acids for use herein are selected from tyrosine, tryptophane, lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine, phenylalanine, proline, glycine, serine, histidine, threonine, methionine, and mixture thereof, most preferably selected from tyrosine, tryptophane, and mixture thereof.
  • Preferred amino acid derivatives are selected from tyrosine ethylate, glycine methylate, tryptophane ethylate, and mixture thereof.
  • Preferred substituted amines and amides for use herein are selected from nipecotamide, N-coco-1,3-propenediamine; N-oleyl-1,3-propenediamine; N-(tallow alkyl)-1,3-propenediamine; 1,4-diamino cyclohexane; 1,2-diaminocyclohexane; 1,12-diaminododecane, and mixtures thereof.
  • glucamines preferably selected from 2,3,4,5,6-pentamethoxy-glucamine; 6-acetylglucamine, glucamine, and mixture thereof.
  • PAMAM Starburst® polyamidoamines
  • Polyamino acid is one suitable and preferred class of amino-functional polymer.
  • Polyaminoacids are compounds which are made up of amino acids or chemically modified amino acids. They can contain alanine, serine, aspartic acid, arginine, valine, threonine, glutamic acid, leucine, cysteine, histidine, lysine, isoleucine, tyrosine, asparagine, methionine, proline, tryptophan, phenylalanine, glutamine, glycine or mixtures thereof.
  • chemically modified amino acids the amine or acidic function of the amino acid has reacted with a chemical reagent.
  • Preferred polyamino acids are polylysines, polyarginine, polyglutamine, polyasparagine, polyhistidine, polytryptophane or mixtures thereof. Most preferred are polylysines or polyamino acids where more than 50% of the amino acids are lysine, since the primary amine function in the side chain of the lysine is the most reactive amine of all amino acids.
  • the preferred polyamino acid has a molecular weight of 500 to 10.000.000, more preferably between 2.000 and 25.000.
  • the polyamino acid can be cross linked.
  • the cross linking can be obtained for example by condensation of the amine group in the side chain of the amino acid like lysine with the carboxyl function on the amino acid or with protein cross linkers like PEG derivatives.
  • the cross linked polyamino acids still need to have free primary and/or secondary amino groups left for reaction with the active ingredient.
  • the preferred cross linked polyamino acid has a molecular weight of 20.000 to 10.000.000, more preferably between 200.000 and 2.000.000.
  • the polyamino acid or the amino acid can be co-polymerized with other reagents like for instance with acids, amides, acyl chlorides. More specifically with aminocaproic acid, adipic acid, ethylhexanoic acid, caprolactam or mixture thereof.
  • the molar ratio used in these copolymers ranges from 1:1 (reagent/ amino acid (lysine)) to 1:20, more preferably from 1:1 to 1:10.
  • the polyamino acid like polylysine can also be partially ethoxylated.
  • polyaminoacids containing lysine, arginine, glutamine, asparagine are given in the Bachem 1996, Peptides and Biochemicals catalog.
  • polyaminoacid can be obtained before reaction with the active ingredient, under a salt form.
  • polylysine can be supplied as polylysine hydrobromide.
  • Polylysine hydrobromide is commercially available from Sigma, Applichem, Bachem and Fluka.
  • Suitable amino functional polymers containing at least one primary and/or secondary amine group for the purpose of the present invention are :
  • the more preferred compounds are selected from ethyl-4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol HF, P, PS, SK, SNA; the diaminobutane dendrimers Astramol® , polylysine, cross-linked polylysine, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched; 1,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.
  • Even most preferred compounds are those selected from ethyl-4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol HF, P, PS, SK, SNA; polylysine, cross-linked polylysine, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched, 1,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.
  • Lupasol like Lupasol HF, P, PS, SK, SNA
  • polylysine cross-linked polylysine, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched, 1,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.
  • such most preferred primary and/or secondary amine compounds also provide fabric appearance benefit, in particular colour appearance benefit, thus providing a resulting amine reaction product with the properties of fabric appearance benefit, deposition onto the surface to be treated, and delayed release of the active as well as release of the perfume composition.
  • the primary and/or secondary amine compound has more than one free primary and/or secondary amine group, several different active ingredients (aldehyde and/or ketone) can be linked to the amine compound.
  • the primary and/or secondary amine compound may also be used as is, i.e. without having been reacted with the above benefit agent like aldehyde and/or ketone perfume ingredient, but with a benefit agent like a perfume composition which is entrapped or embedded within the primary and/or secondary amine compound.
  • the primary and/or secondary amine compound may also be reacted with compounds other than the benefit agent mentioned above like acyl halides, like acetylchloride, palmytoyl chloride or myristoyl chloride, acid anhydrides like acetic anhydride, alkylhalides or arylhalides to do alkylation or arylation, aldehydes or ketones not used as perfume ingredients like formaldehyde, glutaraldehyde, unsaturated ketones, aldehydes or carboxylic acids like 2-decylpropenoic acid, propenal, propenone to form reaction products with the required viscosity.
  • acyl halides like acetylchloride, palmytoyl chloride or myristoyl chloride
  • acid anhydrides like acetic anhydride
  • alkylhalides or arylhalides to do alkylation or arylation
  • aldehydes or ketones not used as perfume ingredients like formaldehyde,
  • the benefit agent is a component that will react with the amino-functional polymer and provide a beneficial effect on the treated surface like fabric upon contact with water or humidity.
  • the benefit agent may be selected from a flavour ingredient, a pharmaceutical ingredient, a biocontrol ingredient, a perfume composition, a refreshing cooling ingredient and mixtures thereof.
  • the benefit agent comprises from 10 to 90%, preferably from 30 to 85%, more preferably from 45 to 80% by weight of the pro-perfume component.
  • Flavour ingredients include spices, flavor enhancers that contribute to the overall flavour perception.
  • Pharmaceutical ingredients include drugs.
  • Biocontrol ingredients include biocides, antimicrobials, bactericides, fungicides, algaecides, mildewcides, disinfectants, antiseptics, insecticides, vermicides, plant growth hormones.
  • Typical antimicrobials include Glutaraldehyde, Cinnamaldehyde, and mixtures thereof.
  • Typical insect and/or moth repellants are perfume ingredients, such as citronellal, citral, N, N diethyl meta toluamide, Rotundial, 8-acetoxycarvotanacetone, and mixtures thereof.
  • Other examples of insect and/or moth repellant for use herein are disclosed in US 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660, 5,196,200, and "Semio Activity of Flavor and Fragrance molecules on various Insect Species", B.D. Mookherjee et al., published in Bioactive Volatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi, R.G. Buttery, and H. Sugisawa, 1993, pp. 35-48.
  • One preferred benefit agent is a perfume ingredient.
  • One typical perfume ingredient is a aldehyde perfume ingredient.
  • the perfume aldehyde is selected from adoxal; anisic aldehyde; cymal; ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T.
  • More preferred aldehydes are selected from citral, 1-decanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1 -carboxaldehyde; cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, trans-2-nonenal, lilial, trans-2-nonenal, and mixture thereof.
  • the perfume ketone is selected from buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so-called lonone, Fleuramone, Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl- Cedrenyl-ketone or Methyl- Cedrylone, Acetophenone, Methyl-Acetophenone, Para-Methoxy-Acetophenone, Methyl-Be
  • the preferred ketones are selected from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, hedione, and mixtures thereof.
  • the benefit agent may also comprise a perfume composition made of mixture of perfume ingredients including or not the above mentioned aldehyde or ketone. This composition is then entrapped within the pro-perfume component by mixing. By such means, a more fully complete perfume formulation can then be deposited onto the contacted surface.
  • Typical of these ingredients include fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
  • natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
  • artificial i.e., a mixture of different nature oils or oil constituents
  • synthetic i.e., synthetically produced odoriferous substances.
  • Such materials are often accompanied by auxiliary materials, such as fixatives, extenders, stabilizers and solvents. These auxiliaries are also included within the meaning of "perfume", as used herein.
  • perfumes are complex mixtures of a plurality of organic compounds.
  • perfume ingredients useful in the perfume compositions include, but are not limited to, amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl- cis -2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl -trans -2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyl
  • fragrance materials include, but are not limited to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether; methyl-beta-naphthylketone; coumarin; 4-tert-butylcyclohexyl acetate; alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; cyclic ethyleneglycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-
  • perfume components are geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal; 2-methyl-3-(
  • Schiff-Bases are the condensation of an aldehyde perfume ingredient with an anthranilate.
  • Typical of Schiff bases are selected from Schiffs base of 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate; condensation products of: hydroxycitronellal and methyl anthranilate; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate; Methyl Anthranilate and HydroxyCitronellal commercially available under the tradename Aurantiol; Methyl Anthranilate and Methyl Nonyl Acetaldehyde commercially available under the tradename Agrumea; Methyl Anthranilate and PT Bucinal commercially available under the tradename Verdanti
  • the perfume ingredients and/or compositions useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
  • the perfume compounds are characterised by having a low Odor Detection Threshold.
  • Odor Detection Threshold ODT
  • GC Gas Chromatography
  • the Odor Detection Threshold is measured according to the following method : The gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chainlength distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated.
  • perfume components are those selected from : 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/or para-methoxy-acetophenone.
  • the perfume ingredients are those as described in WO 96/12785 on page 12-14. Even most preferred are those perfume compositions comprising at least 10%, preferably 25%, by weight of perfume ingredient with an ClogP of at least 2.0, preferably of at least 3.0 and boiling point of at least 250C. Still another preferred perfume composition is a composition comprising at least 20%, preferably 35%, by weight of perfume ingredient with an ClogP at least 2.0, more preferably of at least 3.0 and boiling point of less than or equal to 250C.
  • Clog P is a commonly known calculated measure as defined in the following references "Calculating log P oct from Structures”; Albert Leo (Medicinal Chemistry Project, Pomona College, Claremont, CA USA. Chemical Reviews, Vol. 93, number 4, June 1993; as well as from Comprehensive Medicinal Chemistry, Albert Leo, C. Hansch, Ed. Pergamon Press: Oxford, 1990, Vol. 4, p.315; and Calculation Procedures for molecular lipophilicity: a comparative Study, Quant. Struct. Act. Realt. 15, 403-409 (1996), Raymund Mannhold and Karl Dross.
  • the level of pro-perfume component is of from 10 to 70% by weight, preferably of from 40 to 60% by weight, most preferably of 50% by weight of the pro-perfume composition.
  • a suspending material is another essential element of the present invention. Indeed, a suspending material will provide improved incorporation and stability within the detergent composition, especially liquid detergent compositions.
  • the suspending material when incorporated into aqueous liquid detergent composition, will preferably protect the pro-perfume component from the aqueous medium.
  • the level of suspending aid is of from 30 to 90% by weight, preferably of from 45 to 75% by weight, most preferably of from 50% to 70% by weight of the pro-perfume composition.
  • suspending materials includes liquid as well as solid suspending aid.
  • the liquid suspending material is preferably in a hydrophobic form.
  • hydrophobic means substantially water insoluble.
  • substantially water insoluble shall refer to a material that is not soluble in distilled (or equivalent) water, at 25°C, at a concentration of 0.2% by weight, and preferably not soluble at 0.1% by weight (calculated on a water plus suspending aid weight basis).
  • soluble soluble
  • solubility corresponds to the maximum concentration of suspending material, as applicable, that can dissolve in water or other solvents to form a homogeneous solution, as is well understood to those skilled in the art.
  • Typical of materials that are in hydrophobic form and are useful as suspending materials include ingredients useful in perfumery. Typical of such ingredients are the perfume raw materials, solvents, and mixtures thereof.
  • Typical hydrophobic raw materials include the ketones or aldehydes like hexyl cinnamic aldehyde, hydrocarbons like Limolene, d-Limonene, esters like Hercolyn D, benzyl salicylate, hexyl salicylate, triethyl citrate, iso propyl myristate, or mixtures thereof.
  • Typical hydrophobic solvents include diethyl phtalate, ethers like butoxypropoxypropanol, dipropylene glycol, and mixtures thereof.
  • silicone materials preferably refers to emulsified and/or microemulsified silicones, including those that are commercially available and those that are emulsified and/or microemulsified in the composition, unless otherwise described.
  • silicones which are useful in the present invention are: non-volatile silicone fluids such as polydimethyl siloxane gums and fluids; volatile silicone fluid which can be a cyclic silicone fluid of the formula [(CH3)2SiO]n where n ranges between about 3 to about 7, preferably about 5, linear silicone polymer fluid having the formula (CH3)3SiO[(CH3)2SiO]mSi(CH3)3 where m can be 0 or greater and has an average value such that the viscosity at 25°C of the silicone fluid is preferably about 5 centistokes or less, or silicone polyglycolethers.
  • non-volatile silicone fluids such as polydimethyl siloxane gums and fluids
  • volatile silicone fluid which can be a cyclic silicone fluid of the formula [(CH3)2SiO]n where n ranges between about 3 to about 7, preferably about 5, linear silicone polymer fluid having the formula (CH3)3SiO[(CH3)2SiO]mSi(CH
  • silicones commmercially available from Dow Corning Corporation like the DC 3225C for the silicone glycols ethers, the DC 244 Fluids, DC 245 Fluids, DC 344 Fluids, or DC 345 Fluids, or ABIL K4, ABIL B 8839 for the cyclomethicone, or the DC 200 fluids, ABIL K 520 (hexamethyl disiloxane), ABIL 10 to ABIL 100000 (dimethicone), ABIL AV 8853 (Phenyl dimethicone) for the linear silicones.
  • silicones commmercially available from Dow Corning Corporation like the DC 3225C for the silicone glycols ethers, the DC 244 Fluids, DC 245 Fluids, DC 344 Fluids, or DC 345 Fluids, or ABIL K4, ABIL B 8839 for the cyclomethicone, or the DC 200 fluids, ABIL K 520 (hexamethyl disiloxane), ABIL 10 to ABIL
  • Suitable examples are silicones commercially available from Dow Corning cooperation like DC 3225C, DC5225 and dimethylpolysiloxanes available from Sigma.
  • the suspending material has a viscosity between 250 and 250000 cps, more preferably between 700 and 70000cps. More preferably, the suspending material is selected from benzyl salicylate, diethyl phatalate, dipropylene glycol, butoxypropoxypropanol, silicones, and mixtures thereof, most preferably is selected from silicones.
  • the close physical proximity between the pro-perfume and the suspending aid is obtained by mixing together the reacted amino-functional component and the suspending aid, typically present in a 50:50 weight ratio, under high shear mixing (i.e. 50.000 rpm) using an Ultra Turrax apparatus at a temperature of 50-60°C for 5 minutes.
  • TSE twin Screw Extruder
  • Suitable TSE include the TX-57 MAG, TX-85 MAG, TX-110 MAG, TX-144 MAG, or TX-178 MAG twin screw extruder from Wenger.
  • TX-57 MAG is preferred.
  • TSE suitable for use herein comprise at one of their extremities so called herein after “first part of the TSE” two distinct inlet: one for the active and the other for the amine, and at about the middle of the TSE, so called hereinafter “second part of the TSE” another inlet for the suspending aid. Temperature controllers are also distributed along the TSE.
  • the particle size of the droplet within the detergent composition is of from 1 microns to 50 microns, more preferably from 5 micron to 30 microns, and most preferably of 20 microns.
  • the pro-perfume composition is then incorporated in a detergent composition.
  • Means of incorporation into the detergent composition are conventionally known in the art, and is typically made depending on its end form by either spraying when in sprayable liquid form, or dry-addition, or mixing when in liquid viscous form, e.g. having a viscosity between 100 and 1000 cps. The viscosity is measured on a rheometer, TA Instrument CSL 2 100 at a temperature of 20°C with a gap setting of 500 microns.
  • the pro-perfume composition is incorporated by mixing.
  • Typical level of incorporation of the pro-perfume composition within the detergent composition are of from 0.01 to 10%, more preferably from 0.1 to 5%, and most preferably from 0.2 to 1% by weight of the detergent composition.
  • the detergent composition typically comprises one or more detergent ingredient.
  • the detergent composition is a liquid detergent composition, including aqueous as well as non-aqueous liquid detergent compositions.
  • aqueous and non-aqueous liquid detergent compositions of this invention typically comprises one or more detergent ingredient.
  • Suitable detergent ingredients comprise a surfactant system.
  • the present invention liquid detergent composition comprises non-aqueous, liquid, heavy-duty detergent compositions in the form of a stable suspension of solid, substantially insoluble particulate material dispersed throughout a structured, surfactant-containing liquid phase.
  • the detergent composition comprises from about 49% to 99.95% by weight of the composition of a structured, surfactant-containing liquid phase formed by combining:
  • the major component of the liquid phase of the detergent compositions herein comprises one or more non-aqueous organic diluents.
  • the non-aqueous organic diluents used in this invention may be either surface active, i.e., surfactant, liquids or non-aqueous, non-surfactant liquids referred to herein as non-aqueous solvents.
  • the term "solvent" is used herein to connote the non-surfactant, non-aqueous liquid portion of the compositions herein. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent"-containing liquid phase, other components will be present as particulate material dispersed within the "solvent"-containing liquid phase.
  • the non-aqueous liquid diluent component will generally comprise from about 50% to 100%, more preferably from about 50% to 80%, most preferably from about 55% to 75%, of a structured, surfactant-containing liquid phase.
  • the liquid phase of the compositions herein, i.e., the non-aqueous liquid diluent component will comprise both non-aqueous liquid surfactants and non-surfactant non-aqueous solvents.
  • non-aqueous surfactant liquids which can be used to form the liquid phase of the compositions herein include the alkoxylated alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, alkylpolysaccharides, and the like.
  • Such normally liquid surfactants are those having an HLB ranging from 10 to 16.
  • Most preferred of the surfactant liquids are the alcohol alkoxylate nonionic surfactants.
  • Alcohol alkoxylates are materials which correspond to the general formula: R 1 (C m H 2m O) n OH wherein R 1 is a C 8 - C 16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R 1 is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol materials useful in the liquid phase will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol alkoxylates useful in or as the non-aqueous liquid phase of the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C 12 - C 13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C 9 -C 11 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename.
  • Dobanol 91-5 is an ethoxylated C 9 -C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 -C 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation.
  • the former is a mixed ethoxylation product of C 11 to C 15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
  • Alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company. If alcohol alkoxylate nonionic surfactant is utilized as part of the non-aqueous liquid phase in the detergent compositions herein, it will preferably be present to the extent of from about 1% to 60% of the composition structured liquid phase. More preferably, the alcohol alkoxylate component will comprise about 5% to 40% of the structured liquid phase.
  • an alcohol alkoxylate component will comprise from about 5% to 35% of the detergent composition structured liquid phase. Utilization of alcohol alkoxylate in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of from about 1% to 60% by weight, more preferably from about 2% to 40% by weight, and most preferably from about 5% to 25% by weight, of the composition.
  • Another type of non-aqueous surfactant liquid which may be utilized in this invention are the ethylene oxide (EO) - propylene oxide (PO) block polymers. Materials of this type are well known nonionic surfactants which have been marketed under the tradename Pluronic.
  • non-aqueous surfactant liquid useful in the compositions herein comprises polyhydroxy fatty acid amide surfactants. If present, the polyhydroxy fatty acid amide surfactants are preferably present in a concentration of from about 0.1 to about 8%.
  • Materials of this type of nonionic surfactant are those which conform to the formula: wherein R is a C 9-17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof.
  • Such materials include the C 12 -C 18 N-methyl glucamides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide.
  • the liquid surfactant will comprise from about 50% to 65% of a non-aqueous structured liquid phase. This corresponds to a non-aqueous liquid surfactant concentration in the total composition of from about 15% to 70% by weight, more preferably from about 20% to 50% by weight, of the composition.
  • the liquid phase of the detergent compositions herein may also comprise one or more non-surfactant, non-aqueous organic solvents.
  • non-surfactant non-aqueous liquids are preferably those of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • relatively polar solvents such as ethanol are preferably not utilized.
  • Suitable types of low-polarity solvents useful in the non-aqueous liquid detergent compositions herein do include non-vicinal C 4 -C 8 alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of non-aqueous, low-polarity solvent for use in the compositions herein comprises the non-vicinal C 4 -C 8 branched or straight chain alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol.
  • Hexylene glycol is the most preferred.
  • Another preferred type of non-aqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are especially preferred.
  • Non-aqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred.
  • Yet another preferred type of non-polar, non-aqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: R 1 -C(O)-OCH 3 wherein R 1 ranges from 1 to about 18.
  • Suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the non-aqueous, generally low-polarity, non-surfactant organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • Such a solvent component is preferably utilized in an amount of from about 1% to 70% by weight of the liquid phase.
  • a non-aqueous, low-polarity, non-surfactant solvent will comprise from about 10% to 60% by weight of a structured liquid phase, most preferably from about 20% to 50% by weight, of a structured liquid phase of the composition. Utilization of non-surfactant solvent in these concentrations in the liquid phase corresponds to a non-surfactant solvent concentration in the total composition of from about 1% to 50% by weight, more preferably from about 5% to 40% by weight, and most preferably from about 10% to 30% by weight, of the composition.
  • the ratio of surfactant to non-surfactant liquids e.g., the ratio of alcohol alkoxylate to low polarity solvent, within a structured, surfactant-containing liquid phase can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of surfactant liquid to non-surfactant organic solvent will range about 50:1 to 1:50. More preferably, this ratio will range from about 3:1 to 1:3, most preferably from about 2:1 to 1:2.
  • the non-aqueous liquid phase of the detergent compositions of this invention is prepared by combining with the non-aqueous organic liquid diluents hereinbefore described a surfactant which is generally, but not necessarily, selected to add structure to the non-aqueous liquid phase of the detergent compositions herein.
  • Structuring surfactants can be of the anionic, nonionic, cationic, and/or amphoteric types.
  • Preferred structuring surfactants are the anionic surfactants such as the alkyl sulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzene sulfonates.
  • Carboxylate-type anionics include the C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C 10 -C 18 sarcosinates, especially oleoyl sarcosinate.
  • Yet another common type of anionic surfactant material which may be employed as a structurant comprises other sulfonated anionic surfactants such as the C 8 -C 18 paraffin sulfonates and the C 8 -C 18 olefin sulfonates.
  • Structuring anionic surfactants will generally comprise from about 1% to 30% by weight of the compositions herein.
  • one preferred type of structuring anionic surfactant comprises primary or secondary alkyl sulfate anionic surfactants.
  • Such surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula ROSO 3 - M + wherein R is typically a linear C 8 - C 20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C 10-14 alkyl
  • M is alkali metal.
  • R is about C 12 and M is sodium.
  • Conventional secondary alkyl sulfates may also be utilized as a structuring anionic surfactant for the liquid phase of the compositions herein.
  • Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure: CH 3 (CH 2 ) n (CHOSO 3 - M + ) (CH 2 ) m CH 3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 15, and M is a water-solubilizing cation.
  • alkyl sulfates will generally comprise from about 1% to 30% by weight of the composition, more preferably from about 5% to 25% by weight of the composition.
  • Non-aqueous liquid detergent compositions containing alkyl sulfates, peroxygen bleaching agents, and bleach activators are described in greater detail in Kong-Chan et al.; WO 96/10073; Publiched April 4, 1996, which application is incorporated herein by reference.
  • Another preferred type of anionic surfactant material which may be optionally added to the non-aqueous cleaning compositions herein as a structurant comprises the alkyl polyalkoxylate sulfates.
  • Alkyl polyalkoxylate sulfates are also known as alkoxylated alkyl sulfates or alkyl ether sulfates. Such materials are those which correspond to the formula R 2 -O-(C m H 2m O) n -SO 3 M wherein R 2 is a C 10 -C 22 alkyl group, m is from 2 to 4, n is from about 1 to 15, and M is a salt-forming cation.
  • R 2 is a C 12 -C 18 alkyl, m is 2, n is from about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium.
  • R 2 is a C 12 -C 16
  • m is 2
  • n is from about 1 to 6
  • M is sodium.
  • Ammonium, alkylammonium and alkanolammonium counterions are preferably avoided when used in the compositions herein because of incompatibility with peroxygen bleaching agents.
  • alkyl polyalkoxylate sulfates can also generally comprise from about 1% to 30% by weight of the composition, more preferably from about 5% to 25% by weight of the composition.
  • Non-aqueous liquid detergent compositions containing alkyl polyalkoxylate sulfates, in combination with polyhydroxy fatty acid amides, are described in greater detail in boutique et al; PCT Application No.
  • anionic surfactant for use as a structurant in the compositions herein comprises the linear alkyl benzene sulfonate (LAS) surfactants.
  • LAS surfactants can be formulated into a specific type of anionic surfactant-containing powder which is especially useful for incorporation into the non-aqueous liquid detergent compositions of the present invention.
  • Such a powder comprises two distinct phases. One of these phases is insoluble in the non-aqueous organic liquid diluents used in the compositions herein; the other phase is soluble in the non-aqueous organic liquids.
  • this preferred anionic surfactant-containing powder which can be dispersed in the non-aqueous liquid phase of the preferred compositions herein and which forms a network of aggregated small particles that allows the final product to stably suspend other solid particulate materials in the composition.
  • a preferred anionic surfactant-containing powder is formed by co-drying an aqueous slurry which essentially contains a) one of more alkali metal salts of C 10-16 linear alkyl benzene sulfonic acids; and b) one or more non-surfactant diluent salts. Such a slurry is dried to a solid material, generally in powder form, which comprises both the soluble and insoluble phases.
  • linear alkyl benzene sulfonate (LAS) materials used to form the preferred anionic surfactant-containing powder are well known materials. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C 11-14 , e.g., C 12 , LAS is especially preferred.
  • the alkyl benzene surfactant anionic surfactants are generally used in the powder-forming slurry in an amount from about 20 to 70% by weight of the slurry, more preferably from about 20% to 60% by weight of the slurry.
  • the powder-forming slurry also contains a non-surfactant, organic or inorganic salt component that is co-dried with the LAS to form the two-phase anionic surfactant-containing powder.
  • Such salts can be any of the known sodium, potassium or magnesium halides, sulfates, citrates, carbonates, sulfates, borates, succinates, sulfo-succinates and the like.
  • Sodium sulfate which is generally a bi-product of LAS production, is the preferred non-surfactant diluent salt for use herein. Salts which function as hydrotropes such as sodium sulfo-succinate may also usefully be included.
  • the non-surfactant salts are generally used in the aqueous slurry, along with the LAS, in amounts ranging from about 1 to 50% by weight of the slurry, more preferably from about 5% to 40% by weight of the slurry. Salts that act as hydrotropes can preferably comprise up to about 3% by weight of the slurry.
  • the aqueous slurry containing the LAS and diluent salt components hereinbefore described can be dried to form the anionic surfactant-containing powder preferably added to the non-aqueous diluents in order to prepare a structured liquid phase within the compositions herein.
  • Any conventional drying technique e.g., spray drying, drum drying, etc., or combination of drying techniques, may be employed. Drying should take place until the residual water content of the solid material which forms is within the range of from about 0.5% to 4% by weight, more preferably from about 1% to 3% by weight.
  • the anionic surfactant-containing powder produced by the drying operation constitutes two distinct phases, one of which is soluble in the inorganic liquid diluents used herein and one of which is insoluble in the diluents.
  • the insoluble phase in the anionic surfactant-containing powder generally comprises from about 10% to 45% by weight of the powder, more preferably from about 15% to 35% by weight of a powder.
  • the anionic surfactant-containing powder that results after drying can comprise from about 45% to 94%, more preferably from about 60% to 94%, by weight of the powder of alkyl benzene sulfonic acid salts.
  • Such concentrations are generally sufficient to provide from about 0.5% to 60%, more preferably from about 15% to 60%, by weight of the total detergent composition that is eventually prepared, of the alkyl benzene sulfonic acid salts.
  • the anionic surfactant-containing powder itself can comprise from about 0.45% to 45% by weight of the total composition that is eventually prepared. After drying, the anionic surfactant-containing powder will also generally contain from about 2% to 50%, more preferably from about 2% to 25% by weight of the powder of the non-surfactant salts. After it is dried to the requisite extent, the combined LAS/salt material can be converted to flakes or powder form by any known suitable milling or comminution process.
  • the particle size of this powder will range from 0.1 to 2000 microns, more preferably from about 0.1 to 1000 microns.
  • a structured, surfactant-containing liquid phase of the preferred detergent compositions herein can be prepared by combining the non-aqueous organic diluents hereinbefore described with the anionic surfactant-containing powder as hereinbefore described. Such combination results in the formation of a structured surfactant-containing liquid phase. Conditions for making this combination of preferred structured liquid phase components are described more fully hereinafter in the "Composition Preparation and Use" section.
  • a structured, surfactant-containing liquid phase permits the stable suspension of colored speckles and additional functional particulate solid materials within the preferred detergent compositions of this invention.
  • Additional suitable surfactants for use in the present invention included nonionic surfactants, specifically, polyhydroxy fatty acid amides of the formula: wherein R is a C 9-17 alkyl or alkenyl, R 1 is a methyl group and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S.
  • Preferred surfactants for use in the detergent compositions described herein are amine based surfactants of the general formula: wherein R 1 is a C 6 -C 12 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R 3 and R 4 are individually selected from H, C 1 -C 4 alkyl, or (CH 2 -CH 2 -O(R 5 )) wherein R 5 is H or methyl.
  • Especially preferred amines based surfactants include the following: R 1 -(CH 2 ) 2 -NH 2 R 1 -O-(CH 2 ) 3 -NH 2 R 1 -C(O)-NH-(CH 2 ) 3 -N(CH 3 ) 2 wherein R 1 is a C 6 -C 12 alkyl group and R 5 is H or CH 3 .
  • Particularly preferred amines for use in the surfactants defined above include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, C 8 -C 12 bis(hydroxyethyl)amine, C 8 -C 12 bis(hydroxyisopropyl)amine, C 8 -C 12 amido-propyl dimethyl amine, or mixtures thereof.
  • the amine based surfactant is described by the formula: R 1 -C(O)-NH-(CH 2 ) 3 -N(CH 3 ) 2 wherein R 1 is C 8 -C 12 alkyl.
  • the non-aqueous detergent compositions herein preferably comprise from about 0.01% to 50% by weight, more preferably from about 0.2% to 30% by weight, of solid phase particulate material which is dispersed and suspended within the liquid phase.
  • solid phase particulate material will range in size from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most preferably, such material will range in size from about 5 to 200 microns.
  • the particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the non-aqueous liquid phase of the composition. The types of particulate materials which can be utilized are described in detail as follows:
  • the most preferred type of particulate material useful in the detergent compositions herein comprises particles of a peroxygen bleaching agent.
  • peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
  • Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
  • NAPAA 6-nonylamino-6-oxoperoxycaproic acid
  • Inorganic peroxygen bleaching agents may also be used in particulate form in the detergent compositions herein. Inorganic bleaching agents are in fact preferred.
  • Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials, most preferably the percarbonates.
  • sodium perborate e.g. mono- or tetra-hydrate
  • Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants.
  • coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
  • Inorganic peroxygen bleaching agents e.g., the perborates, the percarbonates, etc.
  • bleach activators which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator.
  • Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November1, 1983 to Chung et al.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group, for example, oxybenzene sulfonate, -OOH, -OOM.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenol sulfonate.
  • Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.
  • Such mixtures are characterized herein as (6-C 8 -C 10 alkamido-caproyl)oxybenzenesulfonate.
  • Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of useful bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
  • peroxygen bleaching agents are used as all or part of the particulate material, they will generally comprise from about 0.1% to 30% by weight of the composition. More preferably, peroxygen bleaching agent will comprise from about 1% to 20% by weight of the composition. Most preferably, peroxygen bleaching agent will be present to the extent of from about 5% to 20% by weight of the composition. If utilized, bleach activators can comprise from about 0.5% to 20%, more preferably from about 3% to 10%, by weight of the composition.
  • activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
  • bleach activators when agglomerated with certain acids such as citric acid, are more chemically stable.
  • organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein.
  • examples of such materials include the alkali metal, citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid.
  • organic phosphonate type sequestering agents such as those which have been sold by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts are highly preferred.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the Sokalan trademark which have molecular weight ranging from about 5,000 to 100,000.
  • Another suitable type of organic builder comprises the water-soluble salts of higher fatty acids, i.e., "soaps".
  • alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • insoluble organic detergent builders can generally comprise from about 2% to 20% by weight of the compositions herein. More preferably, such builder material can comprise from about 4% to 10% by weight of the composition.
  • particulate material which can be suspended in the non-aqueous liquid detergent compositions herein can comprise a material which serves to render aqueous washing solutions formed from such compositions generally alkaline in nature.
  • Such materials may or may not also act as detergent builders, i.e., as materials which counteract the adverse effect of water hardness on detergency performance.
  • suitable alkalinity sources include water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates.
  • water-soluble phosphate salts may also be utilized as alkalinity sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • alkali metal carbonates such as sodium carbonate are the most preferred.
  • the alkalinity source if in the form of a hydratable salt, may also serve as a desiccant in the non-aqueous liquid detergent compositions herein.
  • the presence of an alkalinity source which is also a desiccant may provide benefits in terms of chemically stabilizing those composition components such as the peroxygen bleaching agent which may be susceptible to deactivation by water.
  • the alkalinity source will generally comprise from about 1 % to 25% by weight of the compositions herein. More preferably, the alkalinity source can comprise from about 2% to 15% by weight of the composition.
  • Such materials while water-soluble, will generally be insoluble in the non-aqueous detergent compositions herein. Thus such materials will generally be dispersed in the non-aqueous liquid phase in the form of discrete particles.
  • the non-aqueous liquid detergent compositions herein also essentially contain from about 0.05% to 2%, more preferably 0.1% to 1%, of the composition of colored speckles.
  • Such colored speckles themselves are combinations of a conventional dye or pigment material with a certain kind of carrier material that imparts specific characteristics to the speckles.
  • "colored" speckles are those which have a color that is visibly distinct from the color of the liquid detergent composition in which they are dispersed.
  • the colorant materials which can be used to form the colored speckles can comprise any of the conventional dyes and pigments known and approved for use in detergent products for use in the home.
  • Such materials can include, for example, Ultramarine Blue dye, Acid 80 Blue dye, Red HP Liquitint, Blue Liquitint and the like.
  • Dye or pigment material can be combined with a specific type of carrier material to form the colored speckles for use in the detergent compositions herein.
  • the carrier material is selected to impart to the speckles certain specific density and solubility characteristics.
  • Materials which have been found to be suitable as carriers for the colored speckles include polyacrylates; polysaccharides such as starches, celluloses, gums and derivatives thereof; and polyethylene glycols.
  • Especially preferred carrier material comprises polyethylene glycol having a molecular weight from about 4,000 to 20,000, more preferably from about 4,000 to 10,000.
  • the colored speckles can be produced by dispersing the dye or pigment material within the carrier material. This can be done, for example, by a) melting the carrier and dispersing the dye or pigment therein under mixing, b) mixing the dye/pigment powder and carrier powder together, or c) by dissolving the dye/pigment and the carrier in aqueous solution.
  • the colorant/carrier mixture can then be formed into particles by flaking, spray drying, prilling, extruding or other conventional techniques.
  • the colored speckles will contain from about 0.1% to 5% by weight of the speckles of the colorant (dye or pigment) material.
  • the colored speckles produced in this manner will generally range in size from about 400 to 1,500 microns, more preferably from about 400 to 1,200 microns. Speckles made from the carrier materials specified will have a density less than about 1.4 g/cc, preferably from about 1.0 to 1.4 g/cc. Such speckles will also be substantially insoluble in the non-aqueous liquid phase of the liquid detergent compositions herein. Thus, the colored speckles can be stably suspended in the non-aqueous matrix of the liquid detergent compositions of this invention without dissolving therein. Such speckles, however, rapidly dissolve in the aqueous wash liquors prepared from the liquid detergent compositions herein.
  • the present invention also comprises aqueous based liquid detergent compositions.
  • the aqueous liquid detergent compositions preferably comprise from about 10% to about 98%, preferably from about 30% to about 95%, by weight of an aqueous liquid carrier which is preferably water.
  • the aqueous liquid detergent compositions of the present invention comprise a surfactant system which preferably contains one or more detersive surfactants.
  • the surfactants can be selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, and mixtures thereof.
  • the surfactant system typically comprises from about 5% to about 70%, preferably from about 15% to about 30%, by weight of the detergent composition.
  • Anionic surfactants include C 11 -C 18 alkyl benzene sulfonates (LAS) and primary, branched-chain and random C 10 -C 20 alkyl sulfates (AS), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10 -C 18 alkyl alkoxy sulfates ("AE x S"; especially EO 1-7 ethoxy sulfates), C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylate
  • anionic surfactants useful herein are disclosed in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No. 3,919,678, Laughlin et al, issued December 30, 1975.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • alkyl sulfates especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
  • anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Particularly preferred anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula RO(C 2 H 4 O) x SO 3 - M + wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 1 to about 15.
  • Preferred alkyl sulfate surfactants are the non-ethoxylated C 12-15 primary and secondary alkyl sulfates.
  • fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid.
  • Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
  • Conventional nonionic and amphoteric surfactants include C 12 -C 18 alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy).
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Examples of nonionic surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981.
  • these surfactants include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC 2 H 4 ) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol.
  • Mixtures of anionic and nonionic surfactants are especially useful.
  • Other conventional useful surfactants are listed in standard texts, including C 12 -C 18 betaines and sulfobetaines (sultaines).
  • compositions herein also contain amine oxide surfactants of the formula: R 1 (EO) x (PO) y (BO) z N(O)(CH 2 R') 2 .qH 2 O
  • R 1 (EO) x (PO) y (BO) z N(O)(CH 2 R') 2 .qH 2 O
  • R 1 (EO) x (PO) y (BO) z two short chain moieties, CH 2 R'.
  • R' is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R 1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • R 1 When x+y+z is different from 0, R 1 may be somewhat longer, having a chainlength in the range C 12 -C 24 .
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R 1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
  • Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dihydrate, and mixtures thereof.
  • R' is H
  • the invention further encompasses embodiments wherein R' is CH 2 OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
  • compositions herein also optionally, but preferably, contain up to about 50%, more preferably from about 1% to about 40%, even more preferably from about 5% to about 30%, by weight of a detergent builder material. Lower or higher levels of builder, however, are not meant to be excluded.
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. Detergent builders are described in U.S. Patent No. 4,321,165, Smith et al, issued March 23, 1982. Preferred builders for use in liquid detergents herein are described in U.S. Patent No.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O 2x+1 ⁇ yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a stabilizing agent for oxygen bleaches and as a component of suds control systems.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention.
  • Aluminosilicate builders can be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ) y ] ⁇ xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
  • aluminosilicate ion exchange materials A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
  • polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • Useful succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
  • Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • phosphorus-based builders can be used the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the aqueous and non-aqueous based detergent compositions can, and preferably will, contain various other optional components.
  • Such optional components may be in either liquid or solid form.
  • the optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets.
  • the detergent compositions herein may also optionally contain one or more types of inorganic detergent builders beyond those listed hereinbefore that also function as alkalinity sources.
  • optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as detergent builders are more fully discussed in Corkill et al., U.S. Patent No. 4,605,509; Issued August 12, 1986, the disclosure of which is incorporated herein by reference.
  • crystalline layered silicates such as those discussed in this '509 U.S. patent, are also suitable for use in the detergent compositions herein.
  • optional inorganic detergent builders can comprise from about 2% to 15% by weight of the compositions herein.
  • the detergent compositions herein may also optionally contain one or more types of detergent enzymes.
  • Such enzymes can include proteases, amylases, cellulases and lipases.
  • Such materials are known in the art and are commercially available. They may be incorporated into the non-aqueous liquid detergent compositions herein in the form of suspensions, "marumes" or "prills".
  • Another suitable type of enzyme comprises those in the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP.”
  • Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein. Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Prills in the compositions of the present invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time.
  • compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
  • enzymes will normally be incorporated into the non-aqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, more typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the composition.
  • the non-aqueous liquid detergent compositions herein will typically comprise from about 0.001% to 5%, preferably from about 0.01% to 1% by weight, of a commercial enzyme preparation.
  • Protease enzymes for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • the detergent compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the non-aqueous detergent compositions herein.
  • a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the non-aqueous detergent compositions herein.
  • Such chelating agents thus serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent.
  • Useful chelating agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylene-diamine tetrapropionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanol diglycines.
  • the alkali metal salts of these materials are preferred.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of this invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST.
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof.
  • the chelating agent may, of course, also act as a detergent builder during use of the compositions herein for fabric laundering/bleaching.
  • the chelating agent if employed, can comprise from about 0.1% to 10% by weight of the compositions herein. More preferably, the chelating agent will comprise from about 0.2% to 3% by weight of the detergent compositions herein.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • soil materials can contain from about 0.01% to about 5% by weight of the compositions herein.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • CMC carboxy methyl cellulose
  • the detergent compositions herein may also optionally contain bleach activators which are liquid in form at room temperature and which can be added as liquids to the non-aqueous liquid phase of the detergent compositions herein.
  • One such liquid bleach activator is acetyl triethyl citrate (ATC).
  • ATC acetyl triethyl citrate
  • Other examples include glycerol triacetate and nonanoyl valerolactam.
  • Liquid bleach activators can be dissolved in the non-aqueous liquid phase of the compositions herein.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (CIO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (CIO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech. , (1983), 2, pages 1-94.
  • cobalt pentaamine acetate salts having the formula [Co(NH 3 ) 5 OAc] T y , wherein "OAc" represents an acetate moiety and “T y " is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH 3 ) 5 OAc]Cl 2 ; as well as [Co(NH 3 ) 5 OAc](OAc) 2 ; [Co(NH 3 ) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc]-(SO 4 ); [Co(NH 3 ) 5 OAc](BF 4 ) 2 ; and [Co(NH 3 ) 5 OAc](NO 3 ) 2 (herein "PAC").
  • compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.
  • the detergent compositions herein may also optionally contain conventional brighteners, suds suppressors, dyes and/or perfume materials.
  • Such brighteners, suds suppressors, silicone oils, dyes and perfumes must, of course, be compatible and non-reactive with the other composition components in a non-aqueous environment. If present, brighteners suds suppressors, dyes and/or perfumes will typically comprise from about 0.0001% to 2% by weight of the compositions herein.
  • the non-aqueous liquid detergent compositions herein can also contain from about 0.1% to 5%, preferably from about 0.1% to 2% by weight of a finely divided, solid particulate material which can include silica, e.g., fumed silica, titanium dioxide, insoluble carbonates, finely divided carbon or combinations of these materials.
  • Fine particulate material of this type functions as a structure elasticizing agent in the products of this invention.
  • Such material has an average particle size ranging from about 7 to 40 nanometers, more preferably from about 7 to 15 nanometers.
  • Such material also has a specific surface area which ranges from about 40 to 400m 2 /g.
  • the finely divided elasticizing agent material can improve the shipping stability of the non-aqueous liquid detergent products herein by increasing the elasticity of the surfactant-structured liquid phase without increasing product viscosity. This permits such products to withstand high frequency vibration which may be encountered during shipping without undergoing undesirable structure breakdown which could lead to sedimentation in the product.
  • titanium dioxide the use of this material also imparts whiteness to the suspension of particulate material within the detergent compositions herein. This effect improves the overall appearance of the product.
  • polymeric soil release agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • Examples of polymeric soil release agents useful herein include U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink; U.S.
  • Commercially available soil release agents include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany). Also see U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • polystyrene foam examples include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
  • suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al. If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0% by weight of the detergent compositions.
  • Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967. Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No.
  • dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
  • the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units;
  • x is 0 or 1; and
  • R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI”) are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.)
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • the hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 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.
  • R 1 is anilino
  • R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 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.
  • R 1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor.
  • Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
  • non-aqueous liquid detergent compositions herein are in the form of bleaching agent and/or other materials in particulate form as a solid phase suspended in and dispersed throughout a surfactant-containing, preferably structured non-aqueous liquid phase.
  • the structured non-aqueous liquid phase will comprise from about 45% to 95%, more preferably from about 50% to 90%, by weight of the composition with the dispersed additional solid materials comprising from about 5% to 55%, more preferably from about 10% to 50%, by weight of the composition.
  • the particulate-containing liquid detergent compositions of this invention are substantially non-aqueous (or anhydrous) in character.
  • the amount of water should in no event exceed about 5% by weight of the compositions herein. More preferably, water content of the non-aqueous detergent compositions herein will comprise less than about 1% by weight.
  • the particulate-containing non-aqueous liquid detergent compositions herein will be relatively viscous and phase stable under conditions of commercial marketing and use of such compositions. Frequently the viscosity of the compositions herein will range from about 300 to 5,000 cps, more preferably from about 500 to 3,000 cps. For purposes of this invention, viscosity is measured with a Carrimed CSL2 Rheometer at a shear rate of 20 s -1 .
  • the aqueous based heavy-duty liquid detergent compositions disclosed herein can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the aqueous based heavy-duty liquid detergent compositions of the present invention can be made by mixing and blending the desired ingredients with the desired sovent.
  • the non-aqueous liquid detergent compositions herein can be prepared by first forming the surfactant-containing, preferably structured non-aqueous liquid phase and by thereafter adding to this structured phase the particulate components in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein. In a typical process for preparing such compositions, essential and certain preferred optional components will be combined in a particular order and under certain conditions. In a first step of a preferred preparation process, the anionic surfactant-containing powder used to form the structured, surfactant-containing liquid phase is prepared.
  • This pre-preparation step involves the formation of an aqueous slurry containing from about 30% to 60% of one or more alkali metal salts of linear C 10-16 alkyl benzene sulfonic acid and from about 2% to 30% of one or more diluent non-surfactant salts.
  • this slurry is dried to the extent necessary to form a solid material containing less than about 4% by weight of residual water.
  • this material can be combined with one or more of the non-aqueous organic diluents to form a structured, surfactant-containing liquid phase of the detergent compositions herein.
  • This combination is carried out under agitation conditions which are sufficient to form a thoroughly mixed dispersion of particles of the insoluble fraction of the co-dried LAS/salt material throughout a non-aqueous organic liquid diluent.
  • the non-aqueous liquid dispersion so prepared can then be subjected to milling or high shear agitation under conditions which are sufficient to provide a structured, surfactant-containing liquid phase of the detergent compositions herein.
  • milling or high shear agitation conditions will generally include maintenance of a temperature between about 10°C and 90°C, preferably between about 20°C and 60°C; and a processing time that is sufficient to form a network of aggregated small particles of the insoluble fraction of the anionic surfactant-containing powdered material.
  • Suitable equipment for this purpose includes: stirred ball mills, co-ball mills (Fryma), colloid mills, high pressure homogenizers, high shear mixers, and the like.
  • the colloid mill and high shear mixers are preferred for their high throughput and low capital and maintenance costs.
  • the small particles produced in such equipment will generally range in size from about 0.4 to 2 microns.
  • Milling and high shear agitation of the liquid/solids combination will generally provide an increase in the yield value of the structured liquid phase to within the range of from about 1 Pa to 8 Pa, more preferably from about 1 Pa to 4 Pa.
  • the particulate material to be used in the detergent compositions herein can be added.
  • Such components which can be added under high shear agitation include a silica or titanium dioxide elasticizing agent; particles of substantially all of an organic builder, e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate, can be added while continuing to maintain this admixture of composition components under shear agitation. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
  • an organic builder e.g., citrate and/or fatty acid
  • an alkalinity source e.g., sodium carbonate
  • the particles of the colored speckles and the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
  • the peroxygen bleaching agent material By adding the peroxygen bleaching agent material last, or after all or most of the other components, and especially after alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If enzyme prills are incorporated, they are preferably added to the non-aqueous liquid matrix last.
  • agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity, yield value and phase stability characteristics.
  • compositions of this invention can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions.
  • the aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.
  • suspending aid has been found beneficial in the chemical stability of the pro-perfume within the detergent matrix, whether it being aqueous or non-aqueous. Accordingly, there is provided a the use of the suspending aid for stabilising the pro-perfume component within the detergent composition.
  • a material preferably an aqueous medium like moisture or any other means susceptible of releasing the perfume from the composition.
  • surface it is meant any surface onto which the compound can deposit. Typical examples of such material are fabrics, hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of a perfume such as that with litter like animal litter.
  • the surface is selected from a fabric, a tile, a ceramic; more preferably is a fabric.
  • delayed release is meant release of the benefit agent (e.g perfume) over a longer period of time than by the use of the benefit agent (e.g., perfume) itself.
  • the carrier is a polymer or component which has been chemically reacted with a benefit agent like perfume
  • the release of the benefit agent which is entrapped or embedded within the reacted carrier, i.e. not chemically reacted, is released from the carried benefit agent composition by hydrolysis of the reacted carrier.
  • the hydrolysis of the "protective shell" made by the reacted carrier into the respective aldehyde and/or ketone on the one hand and the polymer on the other will gradually open the shell, thereby enabling release of the entrapped benefit agent.
  • contacting is defined as "intimate contact of a surface with an aqueous solution of the hereinabove described composition.” Contacting typically occurs by soaking, washing, rinsing the composition onto fabric, but can also include contact of a substrate inter alia a material onto which the composition has been absorbed, with the fabric.
  • a reaction vessel of 21 placed on a rotary evaporator, 1500g of ⁇ -Damascone and 1800g of water-free Lupasol WF are mixed together for 4 hours at 42°C at a stirring rate of 20 to100 rpm.
  • the temperature of the reaction mixture, during the mixing, is controlled by means of a water bath and not allowed to go higher than 42°C; the temperature inside the reaction container is of 40°C.
  • the reaction mixture is kept during 16 hours at 42°C under vacuum to remove most of the water from the reaction vessel. 2741g of product is obtained and only traces of unreacted ⁇ -Damascone remain.
  • the viscosity of the obtained pro-perfume component was of 10.000.000cps.
  • perfume mixture Any type of perfume mixture may be used.
  • One preferred composition of the perfume mixture is as follows: Citronellol 7 Geraniol 7 Linalool 7 Para Tertiary Butyl Cyclohexyl Acetate 10 Phenyl Ethyl Alcohol 19 Habanolide 4.5 Para Methoxy Acetophenone 1.5 Benzyl Acetate 4 Eugenol 2 Phenyl Ethyl Acetate 5 Verdyl Acetate 6 Verdyl Propionate 4 Hexyl Cinnamic Aldehyde 3 lonone Gamma Methyl 2 Methyl Cedrylone 10 P.T. Bucinal 7 Para Cresyl Methyl Ether 1
  • the synthesised pro-perfume I or II above mentioned is then mixed with either a silicone glycol ether DC3225C from Dow Corning or an hexamethyl disiloxane (linear silicone) DC 200 fluids with a viscosity of 100cps measured at 20°C from Dow Corning or a dimethylpolysiloxoxane with a viscosity of 60.000 cps from Sigma under high shear mixing (i.e. 50.000 rpm) using an Ultra Turrax apparatus at a temperature of 60°C for 5 minutes.
  • the pro-perfume component and the suspending aid are present in weight ratios of 50:50.
  • the obtained suspension is then added as such to the liquid detergent matrix under low shear mixing (i.e. 200 rpm).
  • the obtained suspension may be subject to creaming on the top, i.e. exhibiting some physical separation. This can be overcome by the addition of Quartz droplets or by adjusting the density as conventionally known by the skilled person.
  • the abbreviated component identifications have the following meanings: LAS Sodium linear alkyl benzene sulfonate MEA Monoethanolamine PG Propanediol BPP Butoxy - propoxy - propanol EtOH Ethanol NaOH Solution of sodium hydroxide NaTS Sodium toluene sulfonate Citric acid Anhydrous citric acid CxyFA C 1x -C 1y fatty acid TPKFA C 12 -C 14 topped whole cut fatty acids.
  • HEDP 1,1-hydroxyethane diphosphonic acid EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt PVNO Polyvinylpyridine-N-Oxide, with an average molecular weight of 50,000.
  • SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloyl backbone 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.
  • Sodium C 12 linear alkyl benzene sulfonate (NaLAS) is processed into a powder containing two phases. One of these phases is soluble in the non-aqueous liquid detergent compositions herein and the other phase is insoluble. It is the insoluble fraction which serves to add structure and particle suspending capability to the non-aqueous phase of the compositions herein.
  • NaLAS powder is produced by taking a slurry of NaLAS in water (approximately 40-50% active) combined with dissolved sodium sulfate (3-15%) and hydrotrope, sodium sulfosuccinate (1-3%). The hydrotrope and sulfate are used to improve the characteristics of the dry powder.
  • a drum dryer is used to dry the slurry into a flake. When the NaLAS is dried with the sodium sulfate, two distinct phases are created within the flake. The insoluble phase creates a network structure of aggregate small particles (0.4-2 um) which allows the finished non-aqueous detergent product to stably suspend solids.
  • the NaLAS powder prepared according to this example has the following makeup shown in Table III.
  • Non-aqueous based heavy duty liquid laundry detergent compositions (I to V) according to the present invention are presented below.
  • Non-Aqueous Liquid Detergent Composition with Bleach Component Wt % I Wt % II Wt % III Wt % IV Wt % V LAS, From Example I 16 13 8 8 2 C24E5 22 25 28 30 34 BPP 19 19 19 19 19 19 Sodium citrate dihydrate 3 3 3 3 3 3 TAED 5.9 5.9 5.9 5.9 5.9 5.9 Sodium carbonate 9 9 9 9 9 MA/AA 3 3 3 3 3 3 3 3 3 Colored speckles 0.4 0.4 0.4 0.4 0.4 0.4 EDDS 1 1 1 1 1 1 1 1 1 1 Cellulase Prills 0.1 0.1 0.1 0.1 0.1 Amylase Prills 0.4 0.4 0.4 0.4 0.4 PAEC 1.3 1.3 1.3 1.3 1.3 1.3 PB1 15 15 15 15 15 15 15 15 PPC1 0.4 - - - - PPC2
  • Table II compositions are stable, anhydrous heavy-duty liquid laundry detergents which provide excellent stain and soil removal performance when used in normal fabric laundering operations whilst still providing good stability of the pro-perfume withn the detergent matrix as well as delayed release of the perfume onto the contacted fabric.
  • Liquid detergent compositions are made according to the following. I II III IV C 25 E3S 2 8 7 5 LAS 15 12 10 8 C 12 -C 14 alkyldimethyl amine oxide - - - 2 C 25 AS 6 4 6 8 C 24 N-methyl glucamide 5 4 3 3 C 24 AE5 6 1 1 1 C 28 FA 11 4 4 3 Citric acid 1 3 3 2 DTPMP 1 1 1 0.5 MEA 8 5 5 2 NaOH 1 2.5 1 1.5 PG 14.5 13.1 10.0 8 EtOH 1.8 4.7 5.4 1 Amylase (300KNU/g) 0.1 0.1 0.1 0.1 0.1 0.1 Lipase D96/L (100KNU/g) 0.15 0.15 0.15 0.15 0.15 Protease (35g/l) 0.5 0.5 0.5 0.5) Endolase 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Cellulase 0.09 0.09 0.09 0.09 SRP1 0.5 - 0.3 0.3 Boric acid 2.4 2.8 2.8 2.4 Sodium
  • liquid detergent compositions (A-D) are found to be very efficient in the removal of a wide range of stains and soils from fabrics under various usage conditions whilst still providing good stability of the pro-perfume withn the detergent matrix as well as delayed release of the perfume onto the contacted fabric.
  • compositions (I to VI) are heavy duty liquid laundry detergent compositions according to the present invention.
  • non-aqueous liquid detergent compositions were prepared in accordance with the present invention : I II III LAS 16.0 16.0 16.0 C23 ESS 21.5 21.5 19.0 Butoxy Propoxy Propanol 18.5 - 16.0 Hexylene Glycol - 18.5 5.0 Sodium citrate dihydrate 6.8 6.8 3.8 [4-[N-nonanoyl-6-aminohexanoyloxy] 6.0 6.0 6.0 benzene sulfonate] Na salt Methyl sulfate salt of methyl quaternized 1.3 1.3 1.3 polyethoxylated hexamethylene diamine EDDS 1.2 1.2 1.2 MA/AA - - 3.0 Sodium Carbonate 10.0 10.0 10.0 10.0 Protease 0.05 0.02 0.02 Amylase 0.01 0.01 0.01 0.01 Cellulase 0.0001 0.0001 PB1 12.0 12.0 12.0 Silicone antifoam 0.75 0.75 1.1 Perfume 1.7 1.7 1.7 Titanium Di
  • aqueous liquid laundry detergent compositions were prepared according to the present invention : I II III IV V VI LAS - - - 1.0 2.0 - C25AS 16.0 13.0 14.0 5.0 - 6.5 C25E3S 5.0 1.0 - 10.0 19.0 3.0 C25E7 2.0 3.5 - 2.5 2.0 5.0 TFAA 5.0 4.5 4.5 6.5 4.0 - APA 2.0 1.0 - 3.0 - 0.5 QAS - - 2.0 - 1.5 - TPKFA 4.5 8.0 15.0 - 5.0 5.0 Citric acid 2.2 3.0 - 0.5 1.0 2.0 Rapeseed fatty acid 2.0 - - 3.0 6.0 1.5 Ethanol 3.2 2.0 2.5 2.2 - 0.5 1,2 Propanediol 5.7 8.5 6.5 7.0 7.0 5.5 Monoethanolamine 5.0 7.5 - 5.0 1.0 2.0 TEPAE - 1.2 - 0.5 0.5 DTPMP - 0.5 - 0.5 - 0.2 HEDP - 0.5 1.0
  • the following spray composition for cleaning of hard surfaces and removing household mildew was prepared according to the present invention : PPC2 0.8 Amylase 0.01 Protease 0.01 Na octyl sulfate 2.0 Na dodecyl sulfate 4.0 Na hydroxide 0.8 Silicate 0.04 Butyl carbitol 4.0 Perfume 0.35 Water/minors up to 100%
  • lavatory cleansing block compositions were prepared according to the present invention.
  • the following toilet bowl cleaning composition was prepared according to the present invention.
  • pre-soak fabric conditioning and/or fabric enhancement compositions according to the present invention which can be suitably used in the laundry rinse cycle.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Cosmetics (AREA)
EP00870069A 2000-01-12 2000-04-13 Composition de pro-parfum Withdrawn EP1116788A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP00870069A EP1116788A1 (fr) 2000-01-12 2000-04-13 Composition de pro-parfum
AU2001230894A AU2001230894A1 (en) 2000-01-12 2001-01-10 Pro-perfume composition
CA002392976A CA2392976A1 (fr) 2000-01-12 2001-01-10 Composition precurseur de parfum
EP01903021A EP1246899A1 (fr) 2000-01-12 2001-01-10 Composition precurseur de parfum
MXPA02006845A MXPA02006845A (es) 2000-01-12 2001-01-10 Composicion de pro-perfume.
PCT/US2001/000822 WO2001051599A1 (fr) 2000-01-12 2001-01-10 Composition precurseur de parfum
BR0107549-7A BR0107549A (pt) 2000-01-12 2001-01-10 Composição de pró-perfume
JP2001551173A JP2003519721A (ja) 2000-01-12 2001-01-10 前香料組成物
CN01803500A CN1394231A (zh) 2000-01-12 2001-01-10 香精原组合物
US10/168,936 US20040018955A1 (en) 2000-01-12 2001-01-10 Pro-perfume composition
ARP010100107A AR026830A1 (es) 2000-01-12 2001-01-11 Composicion de pro-perfume

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP00870004 2000-01-12
EP00870004 2000-01-12
EP00870069A EP1116788A1 (fr) 2000-01-12 2000-04-13 Composition de pro-parfum

Publications (1)

Publication Number Publication Date
EP1116788A1 true EP1116788A1 (fr) 2001-07-18

Family

ID=26074217

Family Applications (2)

Application Number Title Priority Date Filing Date
EP00870069A Withdrawn EP1116788A1 (fr) 2000-01-12 2000-04-13 Composition de pro-parfum
EP01903021A Ceased EP1246899A1 (fr) 2000-01-12 2001-01-10 Composition precurseur de parfum

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP01903021A Ceased EP1246899A1 (fr) 2000-01-12 2001-01-10 Composition precurseur de parfum

Country Status (9)

Country Link
EP (2) EP1116788A1 (fr)
JP (1) JP2003519721A (fr)
CN (1) CN1394231A (fr)
AR (1) AR026830A1 (fr)
AU (1) AU2001230894A1 (fr)
BR (1) BR0107549A (fr)
CA (1) CA2392976A1 (fr)
MX (1) MXPA02006845A (fr)
WO (1) WO2001051599A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033635A1 (fr) * 2001-10-19 2003-04-24 The Procter & Gamble Company Systeme d'administration controle d'un agent avantageux
EP1314777A1 (fr) * 2001-11-27 2003-05-28 The Procter & Gamble Company Compositions précurseur de parfum utilisées dans des produits de nettoyage et traitement de tissus
WO2008017820A1 (fr) * 2006-08-05 2008-02-14 Givaudan Nederland Services B.V. Compositions de parfum
WO2008059189A1 (fr) * 2006-02-28 2008-05-22 Reckitt Benckiser (Uk) Limited Améliorations portant sur ou relatives à des compositions
WO2009153209A1 (fr) * 2008-06-19 2009-12-23 Henkel Ag & Co. Kgaa Précurseur de parfum polymère modifié
WO2011084577A1 (fr) * 2009-12-17 2011-07-14 The Procter & Gamble Company Composition de nettoyage de surfaces dures renfermant un composant de neutralisation des mauvaises odeurs et procédés de nettoyage de surfaces dures
WO2011084322A1 (fr) * 2009-12-17 2011-07-14 The Procter & Gamble Company Procédé de neutralisation des mauvaises odeurs
WO2020188079A1 (fr) * 2019-03-20 2020-09-24 Firmenich Sa Composés pro-parfum encapsulés
WO2022125359A1 (fr) * 2020-12-11 2022-06-16 Dow Silicones Corporation Agent de libération de substance fonctionnelle

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6790815B1 (en) 1998-07-10 2004-09-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6511948B1 (en) 1998-07-10 2003-01-28 The Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6906012B1 (en) 1999-11-09 2005-06-14 Procter & Gamble Company Detergent compositions comprising a fragrant reaction product
US20030134772A1 (en) * 2001-10-19 2003-07-17 Dykstra Robert Richard Benefit agent delivery systems
GB2382586A (en) 2001-12-03 2003-06-04 Procter & Gamble Fabric treatment compositions
US7569530B1 (en) 2003-06-20 2009-08-04 The Procter & Gamble Company Antimicrobial compositions, products and methods employing same
JP2005206726A (ja) * 2004-01-23 2005-08-04 T Hasegawa Co Ltd 水洗トイレ用芳香洗浄剤用香料組成物及びそれを含有する水洗トイレ用芳香洗浄剤
ATE466925T1 (de) * 2005-09-06 2010-05-15 Procter & Gamble Duftverfahren und produkt
US7569529B2 (en) 2005-09-07 2009-08-04 The Procter & Gamble Company Method of using fabric care compositions to achieve a synergistic odor benefit
CN102471739B (zh) 2009-07-09 2016-05-11 宝洁公司 制备香料颗粒的方法
EP3101103B1 (fr) * 2015-06-05 2019-04-24 The Procter and Gamble Company Composition de detergent liquide compacte pour blanchisserie
ES2666186T3 (es) * 2015-06-05 2018-05-03 The Procter & Gamble Company Composición detergente líquida compactada para lavado de ropa
WO2018053356A1 (fr) 2016-09-16 2018-03-22 International Flavors & Fragrances Inc. Compositions de microcapsules stabilisées avec des agents de régulation de viscosité
BR112018016806B1 (pt) 2016-02-18 2021-11-16 International Flavors & Fragrances Inc. Composiqao de microcapsula, e, produtos de consumidor
BR112019003725B1 (pt) * 2016-08-25 2022-08-23 Firmenich S.A Composição de antiperspirante ou desodorante
JP7144821B2 (ja) * 2017-12-11 2022-09-30 株式会社ニイタカ 液体洗浄剤組成物
JP7141301B2 (ja) * 2018-10-11 2022-09-22 花王株式会社 繊維製品用洗浄剤組成物
EP4034073A1 (fr) * 2019-12-20 2022-08-03 Firmenich SA Compositions de proparfum
CN114729287A (zh) * 2019-12-20 2022-07-08 弗门尼舍有限公司 皂组合物
JP7443551B2 (ja) * 2020-03-06 2024-03-05 ザ プロクター アンド ギャンブル カンパニー 芳香プレミックス組成物及び関連する消費者製品
CN111635306B (zh) * 2020-06-12 2022-09-27 上海海益环保科技有限公司 一种芥酸复合稳定剂及制备稳定芥酸的方法
JP2024510569A (ja) * 2021-03-03 2024-03-08 シムライズ アーゲー 香り変化を有するトイレリムブロック
US20230220300A1 (en) * 2022-01-13 2023-07-13 The Procter & Gamble Company Treatment compositions with modified amino acid multimers

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209417A (en) * 1976-08-13 1980-06-24 The Procter & Gamble Company Perfumed particles and detergent composition containing same
JPH04170961A (ja) * 1990-11-02 1992-06-18 Nippon Fine Chem Co Ltd 調合香料
EP0816322A1 (fr) * 1996-06-24 1998-01-07 Givaudan-Roure (International) S.A. Précurseurs de parfums
WO1999043639A1 (fr) * 1998-02-24 1999-09-02 The Procter & Gamble Company Systemes de diffusion de substances brutes de fragrances a base d'alcools tertiaires
WO1999046318A1 (fr) * 1998-03-12 1999-09-16 The Procter & Gamble Company Polymere de silicone precurseur de parfum et ses compositions
EP0971025A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Produits de réaction d'aminé comprenant un ou plusieurs principes actifs
WO2000002987A2 (fr) * 1998-07-10 2000-01-20 The Procter & Gamble Company Composes de reaction d'amine contenant un ou plusieurs ingredients actifs

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU5174000A (en) * 1999-06-01 2000-12-18 Procter & Gamble Company, The Pro-fragrances

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209417A (en) * 1976-08-13 1980-06-24 The Procter & Gamble Company Perfumed particles and detergent composition containing same
JPH04170961A (ja) * 1990-11-02 1992-06-18 Nippon Fine Chem Co Ltd 調合香料
EP0816322A1 (fr) * 1996-06-24 1998-01-07 Givaudan-Roure (International) S.A. Précurseurs de parfums
WO1999043639A1 (fr) * 1998-02-24 1999-09-02 The Procter & Gamble Company Systemes de diffusion de substances brutes de fragrances a base d'alcools tertiaires
WO1999046318A1 (fr) * 1998-03-12 1999-09-16 The Procter & Gamble Company Polymere de silicone precurseur de parfum et ses compositions
EP0971025A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Produits de réaction d'aminé comprenant un ou plusieurs principes actifs
WO2000002987A2 (fr) * 1998-07-10 2000-01-20 The Procter & Gamble Company Composes de reaction d'amine contenant un ou plusieurs ingredients actifs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199231, Derwent World Patents Index; Class D16, AN 1992-254266, XP002166794 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033635A1 (fr) * 2001-10-19 2003-04-24 The Procter & Gamble Company Systeme d'administration controle d'un agent avantageux
EP1314777A1 (fr) * 2001-11-27 2003-05-28 The Procter & Gamble Company Compositions précurseur de parfum utilisées dans des produits de nettoyage et traitement de tissus
WO2003046118A1 (fr) * 2001-11-27 2003-06-05 The Procter & Gamble Company Compositions de proparfum utilisees dans dans des produits de nettoyage ou de traitement de tissus
US6858575B2 (en) 2001-11-27 2005-02-22 Procter & Gamble Company Pro-perfume compositions and substrate-treating products and methods using them
WO2008059189A1 (fr) * 2006-02-28 2008-05-22 Reckitt Benckiser (Uk) Limited Améliorations portant sur ou relatives à des compositions
US9011829B2 (en) 2006-08-05 2015-04-21 Givaudan Nederland Services B.V. Perfume compositions
WO2008017820A1 (fr) * 2006-08-05 2008-02-14 Givaudan Nederland Services B.V. Compositions de parfum
US10722607B2 (en) 2006-08-05 2020-07-28 Givaudan S.A. Perfume compositions
WO2009153209A1 (fr) * 2008-06-19 2009-12-23 Henkel Ag & Co. Kgaa Précurseur de parfum polymère modifié
WO2011084577A1 (fr) * 2009-12-17 2011-07-14 The Procter & Gamble Company Composition de nettoyage de surfaces dures renfermant un composant de neutralisation des mauvaises odeurs et procédés de nettoyage de surfaces dures
WO2011084322A1 (fr) * 2009-12-17 2011-07-14 The Procter & Gamble Company Procédé de neutralisation des mauvaises odeurs
WO2011084574A1 (fr) * 2009-12-17 2011-07-14 The Procter & Gamble Company Composition détergente permettant de laver le linge et renfermant un composant de neutralisation des mauvaises odeurs et procédés de blanchissage d'étoffes
JP2012522626A (ja) * 2009-12-17 2012-09-27 ザ プロクター アンド ギャンブル カンパニー 悪臭中和方法
US20130247941A1 (en) * 2009-12-17 2013-09-26 The Procter & Gamble Company Dishwashing detergent composition having a malodor control component and methods of cleaning dishware
US9055849B2 (en) * 2009-12-17 2015-06-16 The Procter & Gamble Company Dishwashing detergent composition having a malodor control component and methods of cleaning dishware
WO2020188079A1 (fr) * 2019-03-20 2020-09-24 Firmenich Sa Composés pro-parfum encapsulés
US12264295B2 (en) 2019-03-20 2025-04-01 Firmenich Sa Encapsulated pro-perfume compounds
WO2022125359A1 (fr) * 2020-12-11 2022-06-16 Dow Silicones Corporation Agent de libération de substance fonctionnelle

Also Published As

Publication number Publication date
CN1394231A (zh) 2003-01-29
AU2001230894A1 (en) 2001-07-24
BR0107549A (pt) 2002-10-08
CA2392976A1 (fr) 2001-07-19
JP2003519721A (ja) 2003-06-24
WO2001051599A1 (fr) 2001-07-19
AR026830A1 (es) 2003-02-26
EP1246899A1 (fr) 2002-10-09
MXPA02006845A (es) 2002-10-23

Similar Documents

Publication Publication Date Title
EP1144566B1 (fr) Compositions de lessive et de nettoyage
EP1116788A1 (fr) Composition de pro-parfum
EP1123376B2 (fr) Compositions de lessive et de nettoyage
US20040018955A1 (en) Pro-perfume composition
US7601681B2 (en) Laundry and cleaning and/or fabric care composition
EP1095128B1 (fr) Composes de reaction d'amine contenant un ou plusieurs ingredients actifs
US6566312B2 (en) Amine reaction compounds comprising one or more active ingredient
US6790815B1 (en) Amine reaction compounds comprising one or more active ingredient
US20030228992A1 (en) Laundry and cleaning and/or fabric care compositions
US20040147426A1 (en) Laundry and cleaning compositions
MXPA01000290A (en) Laundry and cleaning compositions
MXPA01000292A (en) Laundry and cleaning compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

AKX Designation fees paid
REG Reference to a national code

Ref country code: DE

Ref legal event code: 8566

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20020119