WO2000011134A1 - Dryer-added fabric softener compositions comprising a ternary fragrance delivery system - Google Patents

Dryer-added fabric softener compositions comprising a ternary fragrance delivery system Download PDF

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Publication number
WO2000011134A1
WO2000011134A1 PCT/US1999/019207 US9919207W WO0011134A1 WO 2000011134 A1 WO2000011134 A1 WO 2000011134A1 US 9919207 W US9919207 W US 9919207W WO 0011134 A1 WO0011134 A1 WO 0011134A1
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WIPO (PCT)
Prior art keywords
substituted
unsubstituted
dimethyl
oxo
oil
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PCT/US1999/019207
Other languages
French (fr)
Inventor
Rhonda Jean Jackson
George Kavin Morgan, Iii
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU56868/99A priority Critical patent/AU5686899A/en
Priority to CA002339136A priority patent/CA2339136A1/en
Priority to EP99943851A priority patent/EP1115834A1/en
Publication of WO2000011134A1 publication Critical patent/WO2000011134A1/en

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation

Definitions

  • the present invention relates to dryer-added fabric treatment compositions which comprise a fragrance delivery system having enhanced fragrance longevity benefits for fabric.
  • the fragrance delivery system is a ternary system comprising one or more free perfume ingredients, a perfume admixture complexed with one or more cyclodextrins, and one or more ⁇ -ketoester pro-fragrances.
  • dryer-added fabric conditioning formulators have attempted to deliver a "fresh” or “clean” odor to washed clothing via the automatic dryer to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective.
  • Dryer-added substrates are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer and which attempt to deliver a prolonged "fragrance” or “pleasurable smell” to fabric which has been laundered via automatic appliance.
  • fragrance raw materials are delivered to fabric by way of a substrate added fabric conditioning composition comprising one or more pro-fragrance compounds having high fabric substantivity and delayed release of fragrance.
  • the present invention meets the aforementioned needs in that it has been surprisingly discovered that fragrance raw materials can be delivered onto fabric "via dryer-added fabric conditioners" by way of a ternary component fragrance delivery system having high fabric substantivity and that the materials which comprise this system are capable of releasing their fragrance raw materials thereby imparting a "fresh" or “clean” aesthetic odor benefit to the fabric for an extended period of time. Therefore, in addition to the short-term pleasurable odor benefits, the fragrance delivery systems according to the present invention continue to release their fragrance raw materials for as long as several weeks depending upon the selection of delivery system components.
  • the first aspect of the present invention relates to dryer-added fabric conditioning compositions comprising:
  • a fabric conditioning composition said composition disposed on said sheet, and said composition comprising: a) from about 1% to about 80% by weight, of a fabric softening active; b) from about 0.1% by weight, of a fragrance delivery system, said fragrance delivery system comprising: i) from about 1% to about 50% by weight, of a ⁇ -ketoester pro- fragrance; ii) from about 50% to about 99% by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from about 8% to about 18% by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from about 1% to about 90% by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; iv) the balance carriers; c) from about 0.01 % by weight, of a fabric color care agent; and d) the balance carriers and adjunct ingredients.
  • the present invention also relates to methods for providing extended fragrance benefits to fabric by contacting fabric in an automatic dryer with the fragrance delivery systems of the present invention.
  • the preset invention relates to dryer-added fabric softener compositions which provided an enhanced perfume or fragrance benefit to the consumer.
  • the novel fragrance delivery system of the present invention insures that the fabric will retain a pleasurable aesthetic quality for days, preferably weeks after the fabric has been treated by the dry-added material.
  • the dryer added fabric softening compositions of the present invention are deposited upon a substrate, preferably a sheet, and are used to provide an enhanced perfume benefit to fabric.
  • the fabric softening compositions of the present invention comprise from about 0.1%), preferably from about 1%, more preferably from about 5%, most preferably from about 10%) to about 20%, more preferably to about 15%> by weight, of a fragrance delivery system as described herein.
  • the fragrance delivery system of the present invention is a ternary component system wherein fragrance raw materials are delivered to fabric via three "vectors" or in three ways: a) by way of one or more cyclodextrin inclusion complexes; b) by way of an uncomplexed fragrance raw material admixture; and c) by way of a pro-fragrance.
  • the fragrance delivery system of the present invention comprises from about 50%, preferably from about 55%), more preferably from about 60%>, most preferably from about 65%> to about 99%>, preferably to about 95%>, more preferably to about 90% by weight of a cyclodextrin inclusion complex which comprises one or more fragrance raw materials which are complexed with one or more cyclodextrins.
  • the loading of fragrance raw materials in the cyclodextrin complexes of the present invention is from about 8%> to about 18%.
  • cyclodextrin includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-, beta-, gamma-cyclodextrins, and mixtures thereof, and/or their derivatives, and/or mixtures thereof, that are capable of forming inclusion complexes with fragrance raw materials or pro-accords.
  • the specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume.
  • the "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic.
  • the unique shape and physical-chemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules such as fragrance raw material molecules which can fit into the cavity.
  • the fragrance raw material/cyclodextrin complex is thus an example of molecular encapsulation.
  • Beta-cyclodextrin is the most preferred cyclodextrin and the one whose complex benefits most from its affinity to form inclusion complexes.
  • Alpha-, beta-, and gamma- cyclodextrins can be obtained from, among others, Cerestar USA, Inc., Hammond, Indiana and Wacker Chemicals (USA), Inc., New Canaan, Connecticut .
  • cyclodextrin derivatives suitable for use herein are methyl- ⁇ -CD, hydroxyethyl- ⁇ -CD, and hydroxypropyl- ⁇ -CD of different degrees of substitution (DS), available from, among others, Cerestar USA Inc., Hammond, Indiana, Aldrich Chemical Company, Milwaukee, Wisconsin; Wacker Chemicals (USA), New Canaan, Connecticut; and Chinoin Pharmaceutical Works, Budapest, Hungary. Water-soluble derivatives are also highly desirable.
  • the individual cyclodextrins can also be linked together, e.g., using multifunctional agents to form oligomers, polymers, etc. Examples of such materials are available commercially from Cerestar USA and from Aldrich Chemical Company ( ⁇ - CD/epichlorohydrin copolymers).
  • Mixtures of cyclodextrins can conveniently be obtained by using intermediate products from known processes for the preparation of cyclodextrins including those processes described in U.S. 3,425,910, Armbruster et al, issued February 4, 1969; U.S. 3,812,01 1, Okada et al, issued May 21, 1974; U.S. 4,317,881, Yagi et al, issued March 2, 1982; U.S. 4,418,144, Okada et al, issued November 29, 1983; and U.S. 4,738,923, Ammeraal, issued April 19, 1988, all of said patents being incorporated herein by reference.
  • cyclodextrins are alpha-cyclodextrin, beta-cyclodextrin, and/or gamma-cyclodextrin, more preferably beta-cyclodextrin.
  • Some cyclodextrin mixtures are commercially available from, e.g., Ensuiko Sugar Refining Company, Yokohama, Japan.
  • the fragrance delivery systems of the present invention comprise a fragrance raw material admixture component which comprises one or more fragrance raw materials which are added directly the fabric softener composition.
  • the compositions of the present invention comprise from about 1%>, preferably from about 5%, more preferably from about 20% to about 90%), preferably to about 70%>, more preferably to about 50% by weight, of the fragrance delivery system, a fragrance raw material admixture.
  • fragrance raw materials are herein defined as compounds having a molecular weight of at least 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent either alone or in combination with other "fragrance raw materials”.
  • fragment raw materials comprise inter alia alcohols, ketones, aldehydes, esters, ethers, nitriles, and cyclic and acyclic alkenes such as terpenes.
  • a listing of common "fragrance raw materials” can be found in various reference sources, for example, “Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and “Perfumes: Art, Science and Technology”; M ⁇ ller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) both incorporated herein by reference.
  • fragrance raw material alcohols suitable for use as fragrance raw materials of the present invention include 2,4-dimethyl-3-cyclohexene-l-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-l- methylethenylbicyclo[2.2.1]hept-5-ene-2-methanol (Arbozol), 2,4,6-trimethyl-3-cyclohexene-l- methanol (Isocyclo geraniol), 4-(l-methylethyl)cyclohexanemethanol (Mayol), -3,3-trimethyl- 2-norborane methanol, 1,1 -dimethyl- l-(4-methylcyclohex-3-enyl)methanol, 2-phenylethanol, 2- cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p
  • Non-limiting examples of fragrance raw material aldehydes suitable for use in the fragrance delivery system according to the present invention include phenylacetaldehyde, p- methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methylnonyl acetaldehyde, phenylpropanal, 3-(4-t-butylphenyl)-2-methyl propanal (Lilial), 3-(4-t-butylphenyl)-propanal (Bourgeonal), 3-(4-methoxyphenyl)-2-methylpropanal (Canthoxal), 3-(4-isopropylphenyl)-2- methylpropanal (Cymal), 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (Helional), 3-(4- ethylpheny)-2,2-dimethylpropanal (Floralozone), phenylbutanal, 3-methyl-5-phenyl
  • Non-limiting examples of fragrance raw material ketones suitable for use in the fragrance delivery systems according to the present invention include -damascone, ⁇ - damascone, ⁇ -damascone, ⁇ -damascenone, muscone, 6,7-dihydro-l,l,2,3,3-pentamethyl-4(5H)- indanone (cashmeran), c/s-jasmone, dihydrojasmone, ⁇ -ionone, ⁇ -ionone, dihydro- ⁇ -ionone, ⁇ - methyl ionone, -wo-methyl ionone, 4-(3,4-methylenedioxyphenyl)butan-2-one, 4-(4- hydroxyphenyl)butan-2-one, methyl ⁇ -naphthyl ketone, methyl cedryl ketone, 6-acetyl- 1,1,2,4,4,7-hexamethyltetralin (tonalid), /-car
  • Non-limiting examples of fragrance raw material esters suitable for use in the fragrance delivery systems according to the present invention include geranyl formate, citronellyl formate, phenylethyl formate, phenoxyethyl formate, tr ⁇ «s-2-hexenyl formate, c/s-3-hexenyl formate, cw-6-nonenyl formate, 9-decenyl formate, 3,5,5-trimethylhexyl formate, 3-methyl-5- phenylpentanyl formate, 6-methylheptan-2-yl formate, 4-(2,2,6-trimethyl-2-cyclohexen-l-yl)-3- buten-2-yl formate, 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-l-yl)-4-penten-2-yl formate, 4- isopropylcyclohexyleth-2-yl formate, 6,8-dimethylnonan-2-yl formate, de
  • the fragrance delivery systems according to the present invention comprise from about 1%), preferably from about 2% to about 50%, preferably to about 25% by weight, of one or more ⁇ -ketoesters pro- fragrances having the formula:
  • R is alkoxy derived from a fragrance raw material alcohol.
  • fragrance raw material alcohols are described herein above.
  • Most preferred alcohols which are delivered via a ⁇ -ketoester pro-fragrance are linalool, dihydromyrcenol, and mixtures thereof.
  • Rl, R and R ⁇ are each independently hydrogen, C ] -C3 ⁇ substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, Cg-C3Q substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstitute
  • R ⁇ , R5, and R ⁇ are each independently hydrogen, C1 -C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1 -C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy,
  • R*, R or R ⁇ units are hydrogen.
  • R % R- and R" units are each hydrogen.
  • the remaining unit is C1 -C20 substituted or unsubstituted linear alkyl, C3-C20 substituted or unsubstituted branched alkyl, C3-C20 substituted or unsubstituted cyclic alkyl; more preferably methyl.
  • R" are taken together to form a C6-C30 substituted or unsubstituted aryl unit, preferably substituted or unsubstituted phenyl and naphthyl.
  • substituted as it applies to linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl, branched alkenyl, cyclic alkenyl, branched alkoxy, cyclic alkoxy, alkynyl, and branched alkynyl units are defined as "carbon chains which comprise substitutents other than branching of the carbon atom chain", for example, other than the branching of alkyl units (e.g.
  • Non-limiting examples of "substituents” include hydroxy, C1 -C12 alkoxy, preferably methoxy; C3-C12 branched alkoxy, preferably isopropoxy; C3-C12 cyclic alkoxy; nitrilo; halogen, preferably chloro and bro o, more preferably chloro; nitro; morpholino; cyano; carboxyl, non-limiting examples of which are - CHO; -C0 2 -M + , -C0 2 R 9 ; -CONH 2 ; -CONHR 9 ; -CONR 9 2 ; wherein R 9 is C ⁇ -C 12 linear or branched alkyl); -S0 3 " M + ; -OSO3- M + ; -N(R 10 ) ; and -N + (R 10 ) 3 ⁇ - wherein each R 10 is independently hydrogen or C1 -C4 alkyl;
  • the preferred pro-fragrance according to the present invention is 3,7-dimethyl-l,6- octadien-3-yl 3-( ⁇ -naphthyl)-3-oxo-propionate which delivers the fragrance raw material alcohol linalool.
  • compositions of the present invention comprise at least about 1%>, preferably from about 10%), more preferably from about 20% to about 80%>, more preferably to about 60%> by weight, of the composition of one or more fabric softener actives.
  • the preferred fabric softening actives according to the present invention are amines having the formula:
  • each R is independently Ci -Cg alkyl, Ci -Cg hydroxyalkyl, benzyl, and mixtures thereof;
  • R ⁇ is preferably C1 1 -C22 linear alkyl, C] i -C22 branched alkyl, C] i -C22 linear alkenyl, C1 1-C22 branched alkenyl, and mixtures thereof;
  • Q is a carbonyl moiety independently selected from the units having the formula: 0 0 R 2 0 0 R 2
  • X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
  • the anion can also, but less preferably, carry a double charge, in which case X' " ) represents half a group.
  • the index m has a value of from 1 to 3; the index n has a value of from 1 to 4, preferably 2 or 3, more preferably 2.
  • One embodiment of the present invention provides for amines and quaternized amines having two or more different values for the index n per molecule, for example, a softener active prepared from the starting amine methyl(3-aminopropyl)(2-hydroxyethyl)amine.
  • More preferred softener actives according to the present invention have the formula:
  • R 1 is a fatty acyl moiety.
  • Suitable fatty acyl moieties for use in the softener actives of the present invention are derived from sources of triglycerides including tallow, vegetable oils and/or partially hydrogenated vegetable oils including inter alia canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil. Yet more preferred are the Diester Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2.
  • DEQA's Diester Quaternary Ammonium Compounds
  • the R! units are typically mixtures of linear and branched chains of both saturated and unsaturated aliphatic fatty acids, an example of which (canola oil), is described in Table I herein below.
  • the formulator can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of triglyceride to form a "customized blend".
  • the fatty acyl composition may vary, as in the case of vegetable oil, from crop to crop, or from variety of vegetable oil source to variety of vegetable oil source.
  • DEQA's which are prepared using fatty acids derived from natural sources are preferred.
  • a preferred embodiment of the present invention provides softener actives comprising R units which have at least about 3%>, preferably at least about 5%, more preferably at least about 10%), most preferably at least about 15%> C1 1-C22 alkenyl, including polyalkenyl (polyunsaturated) units wter alia oleic, linoleic, linolenic.
  • mixed chain fatty acyl units is defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains having from 10 carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case of alkenyl chains, from one to three double bonds, preferably all double bonds in the cis configuration".
  • R* units of the present invention it is preferred that at least a substantial percentage of the fatty acyl groups are unsaturated, e.g., from about 25%), preferably from about 50%) to about 70%), preferably to about 65%.
  • the total level of fabric softening active containing polyunsaturated fatty acyl groups can be from about 3%, preferably from about 5%, more preferably from about 10% to about 30%>, preferably to about 25%, more preferably to about 18%>.
  • cis and trans isomers can be used, preferably with a cisltrans ratio is of from 1 :1, preferably at least 3:1, and more preferably from about 4:1 to about 50: 1, more preferably about 20: 1, however, the minimum being 1 : 1.
  • the level of unsaturation contained within the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
  • IV Iodine Value
  • a cisltrans isomer weight ratio greater than about 30/70, preferably greater than about 50/50 and more preferably greater than about 70/30 provides optimal concentrability.
  • a further preferred embodiment of the present invention comprises DEQA's wherein the average Iodine Value for R ⁇ is approximately 45.
  • the R! units suitable for use in the isotropic liquids present invention can be further characterized in that the Iodine Value (IV) of the parent fatty acid, said IV is preferably from about 10, more preferably from about 50, most preferably from about 70, to a value of about 140, preferably to about 130, more preferably to about 115.
  • formulators may wish to add an amount of fatty acyl units which have Iodine Values outside the range listed herein above. For example, "hardened stock" (IV less than or equal to about 10) may be combined with the source of fatty acid admixture to adjust the properties of the final softener active.
  • a prefered source of fatty acyl units especially fatty acyl units having branching, for example, "Guerbet branching", methyl, ethyl, etc. units substituted along the primary alkyl chain
  • synthetic sources of fatty acyl units are also suitable.
  • the formulator may with to add one or more fatty acyl units having a methyl branch at a "non-naturally occuring" position, for example, at the third carbon of a C17 chain.
  • acyl units whihc are not found in significant (greater than about 0.1%) quantities is common fats and oils which serve as feedstocks for the source of triglycerides described herein.” If the desired branched chain fatty acyl unit is unavailable from readily available natural feedstocks, therefore, synthetic fatty acid can be suitably admixed with other synthetic materials or with other natural triglyceride derived sources of acyl units.
  • N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy-ethyl)-N,N- dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
  • compositions of the present invention preferably comprise a color care agent.
  • the composition comprises from about 0.01%, preferably from about 0.1%o, more preferably from about 0.5%) to about 20%, more preferably to about 10%>, most preferably to about 7% by weight, of a color care agent.
  • Preferred color care agents have the formula:
  • R 1 , R 2 , R 3 , and R 4 are each independently selected from the group consisting of hydrogen; C,-C 10 linear or branched alkyl; C r C 10 linear or branched alkenyl; C,-C 10 linear or branched alkyl which is substituted by one or more hydroxyl units; C,-C 10 linear or branched alkenyl which is substituted by one or more hydroxyl units; an alkyleneoxy unit having the formula: (R 5 OMR 6 0) y R 7 wherein R 5 is 1,2-propylene, 1,3-propylene, 1 ,4-butylene, and mixtures thereof, R 6 is ethylene, R 7 is hydrogen, C r C 10 linear or branched alkyl, and mixtures thereof, x is an integer form 0 to 50, y is an integer from 0 to 50; alkyleneamine units having the formula
  • R 8 and R 9 are each independently selected from the units which comprise R 1 .
  • Preferred R 1 , R 2 , R 3 , and R 4 are hydrogen, 2-hydroxypropyl, alkyleneoxy units, alkyleneamine units and mixtures thereof.
  • a prefered color care agent is N,N,N',N'-tetrakis-(2- hydroxypropyl)ethylenediamine.
  • X is hydrogen, hydroxy, C,-C 10 linear or branched alkyl, and mixtures thereof, preferably hydrogen.
  • the index n is an integer from 1 to 6.
  • compositions of the present invention may also optionally comprise one or more adjunct ingredients.
  • adjunct ingredients are selected from the group consisting of chelating agents, cationic charge boosters, dispersibility aids, soil release agents, nonionic fabric softening agents, preservatives, colorants, optical brighteners, opacifiers, anti- shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof.
  • One aspect of the present invention relates to fabric enhancement compositions which are delivered to fabric via dryer-added substrate.
  • the present invention encompasses articles of manufacture. Representative articles are those that are adapted to soften fabrics in an automatic laundry dryer, of the types disclosed in U.S. Patent 3,989,631, Marsan, issued Nov. 2, 1976; U.S. Patent 4,055,248, Marsan, issued Oct. 25, 1977; U.S. Patent 4,073,996, Bedenk et al., issued Feb. 14, 1978; U.S. Patent 4,022,938, Zaki et al., issued May 10, 1977; U.S. Patent 4,764,289, Trinh, issued Aug. 16, 1988; U.S.
  • the fabric treatment compositions are provided as an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer.
  • a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer.
  • Such dispensing means can be designed for single usage or for multiple uses.
  • the dispensing means can also be a "material" that releases the fabric softener composition and then is dispersed and/or exhausted from the dryer.
  • a highly preferred article herein comprises the fabric treatment composition releasably affixed to a flexible substrate in a sheet configuration.
  • Highly preferred paper, woven or nonwoven "absorbent" substrates useful herein are fully disclosed in U. S. Patent 3,686,025, Morton, issued August 22, 1972, incorporated herein by reference. It is known that most substances are able to absorb a liquid substance to some degree; however, the term "absorbent” as used herein, is intended to mean a substance with an absorbent capacity (i.e., a parameter representing a substrate's ability to take up and retain a liquid) from 4 to 12, preferably, 5 to 7, times its weight of water.
  • an absorbent capacity i.e., a parameter representing a substrate's ability to take up and retain a liquid
  • draining time is 15 seconds instead of 1 minute
  • the specimen is immediately weighed on a torsion balance having a pan with turned-up edges.
  • Absorbent capacity values are then calculated in accordance with the formula given in said Specification. Based on this test, one-ply, dense bleached paper (e.g., kraft or bond having a basis eight of about 32 pounds per 3,000 square feet) has an absorbent capacity of 3.5 to 4, commercially available household one-ply toweling paper has a value of 5 to 6; and commercially available two-ply household toweling paper has a value of 7 to about 9.5.
  • one-ply, dense bleached paper e.g., kraft or bond having a basis eight of about 32 pounds per 3,000 square feet
  • absorbent capacity 3.5 to 4
  • commercially available household one-ply toweling paper has a value of 5 to 6
  • commercially available two-ply household toweling paper has a value of 7 to about 9.5.
  • Using a substrate with an absorbent capacity of less than 4 tends to cause too rapid release of the fabric treatment composition from the substrate resulting in several disadvantages, one of which is uneven conditioning of the fabrics.
  • Using a substrate with an absorbent capacity over 12 is undesirable, inasmuch as too little of the fabric treatment composition is released to condition the fabrics in optimal fashion during a normal drying cycle.
  • Such a substrate comprises a nonwoven cloth having an absorbent capacity of preferably from about 5 to 7 and wherein the weight ratio of fabric treatment composition to substrate on a dry weight basis ranges from about 5:1 to 1 : 1.
  • Non-woven cloth substrate preferably comprises cellulosic fibers having a length of from 3/16 inch to 2 inches a denier of from 1.5 to 5 and the substrate is adhesively bonded together with a binder resin.
  • the flexible substrate preferably has openings sufficient in size and number to reduce restriction by said article of the flow of air through an automatic laundry dryer.
  • the better openings comprise a plurality of rectilinear slits extended along one dimension of the substrate.
  • the dispensing means will normally carry an effective amount of fabric treatment composition.
  • Such effective amount typically provides sufficient fabric conditioning agent and or anionic polymeric soil release agent for at least one treatment of a minimum load in an automatic laundry dryer.
  • Amounts of fabric treatment composition for multiple uses, e.g., up to about 30, can be used.
  • Typical amounts for a single article can vary from about 0.25g to about 100 gm.
  • One such article comprises sponge material releasably enclosing enough fabric treatment composition to effectively impart fabric soil release and softness benefits during several cycles of clothes.
  • This multi-use article can be made by filling a hollow sponge with about 20 gms of the fabric treatment composition.
  • the substrate embodiment of this invention can be used for imparting the above- described fabric treatment composition to fabric to provide softening and/or antistatic effects together with color fidelity benefits to fabric in an automatic laundry dryer.
  • the method of using the composition of the present invention comprises: commingling pieces of damp fabric by tumbling said fabric under heat in an automatic clothes dryer with an effective amount of the fabric treatment composition.
  • the present invention also relates to a method for using the fragrance delivery system of the present invention to provide fabric with enhanced fragrance longevity benefits delivered via the automatic dryer.
  • the method comprises the step of contacting clothing in an automatic dryer with an article of manufacture which comprises:
  • a fabric conditioning composition said composition disposed on said sheet, and said composition comprising: a) from about 1% to about 80% by weight, of a fabric softening active; b) from about 0.1 % by weight, of a fragrance delivery system, said fragrance delivery system comprising: i) from about 1%> to about 50%> by weight, of 3,7-dimethyl-l,6- octadien-3-yl 3-( ⁇ -naphthyl)-3-oxo-propionate; ii) from about 50% to about 99%> by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from about 8%> to about 18% by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from about 1%> to about 90% by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; iv) the fragrance delivery
  • Lithium diisopropylamide (101.0 mL of a 2.0 M solution, 0.202 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. 3,7-Dimethyl- l,6-octadien-3-yl acetate (linalyl acetate) in the amount of (18.66 g, 0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min.
  • the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of (17.43 g, 0.090 mol) dissolved in THF (25 mL) over 30 min.
  • the mixture is warmed to -20 °C and stirred at that temperature for 18 h.
  • the mixture is quenched with 20%> HCl (53 mL).
  • the mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL).
  • compositions illustrate the fabric conditioning compositions which are then deposed upon a substrate material.

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Abstract

The present invention relates to dryer-added fabric conditioning compositions which comprises a fabric softening agent, a color care agent and a fragrance delivery system having enhanced perfume and fragrance longevity benefits, said fragrance delivery system comprising: i) from about 1 % to about 50 % by weight, of a β-ketoester pro-fragrance; ii) from about 1 % to about 50 % by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from about 8 % to about 18 % by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from about 1 % to about 90 % by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; and iv) the balance carriers.

Description

DRYER-ADDED FABRIC SOFTENER COMPOSITIONS COMPRISING A TERNARY FRAGRANCE DELIVERY SYSTEM
FIELD OF THE INVENTION
The present invention relates to dryer-added fabric treatment compositions which comprise a fragrance delivery system having enhanced fragrance longevity benefits for fabric. The fragrance delivery system is a ternary system comprising one or more free perfume ingredients, a perfume admixture complexed with one or more cyclodextrins, and one or more β-ketoester pro-fragrances.
BACKGROUND OF THE INVENTION
In addition to providing fabric with anti-static, softness, and color fidelity benefits, dryer-added fabric conditioning formulators have attempted to deliver a "fresh" or "clean" odor to washed clothing via the automatic dryer to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective. Dryer-added substrates are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer and which attempt to deliver a prolonged "fragrance" or "pleasurable smell" to fabric which has been laundered via automatic appliance.
Attempts have been made to deliver perfume ingredients, especially fragrance raw material alcohols and ketones, which have an enduring fragrance benefit, from fabric conditioning compositions which are delivered from a substrate article inter alia a sheet. The admixture of fragrance and perfume raw materials into a perfume component, which is subsequently deposed upon a substrate, may provide a short-term fragrance benefit, however, these materials have, in general, fail to provide a lasting fragrance benefit to fabric.
Accordingly, there remains a need in the art for a fragrance delivery system wherein fragrance raw materials are delivered to fabric by way of a substrate added fabric conditioning composition comprising one or more pro-fragrance compounds having high fabric substantivity and delayed release of fragrance.
SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has been surprisingly discovered that fragrance raw materials can be delivered onto fabric "via dryer-added fabric conditioners" by way of a ternary component fragrance delivery system having high fabric substantivity and that the materials which comprise this system are capable of releasing their fragrance raw materials thereby imparting a "fresh" or "clean" aesthetic odor benefit to the fabric for an extended period of time. Therefore, in addition to the short-term pleasurable odor benefits, the fragrance delivery systems according to the present invention continue to release their fragrance raw materials for as long as several weeks depending upon the selection of delivery system components.
The first aspect of the present invention relates to dryer-added fabric conditioning compositions comprising:
A) a substrate in the form of a sheet; and
B) a fabric conditioning composition, said composition disposed on said sheet, and said composition comprising: a) from about 1% to about 80% by weight, of a fabric softening active; b) from about 0.1% by weight, of a fragrance delivery system, said fragrance delivery system comprising: i) from about 1% to about 50% by weight, of a β-ketoester pro- fragrance; ii) from about 50% to about 99% by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from about 8% to about 18% by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from about 1% to about 90% by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; iv) the balance carriers; c) from about 0.01 % by weight, of a fabric color care agent; and d) the balance carriers and adjunct ingredients.
The present invention also relates to methods for providing extended fragrance benefits to fabric by contacting fabric in an automatic dryer with the fragrance delivery systems of the present invention. These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION The preset invention relates to dryer-added fabric softener compositions which provided an enhanced perfume or fragrance benefit to the consumer. The novel fragrance delivery system of the present invention insures that the fabric will retain a pleasurable aesthetic quality for days, preferably weeks after the fabric has been treated by the dry-added material.
The dryer added fabric softening compositions of the present invention are deposited upon a substrate, preferably a sheet, and are used to provide an enhanced perfume benefit to fabric. The fabric softening compositions of the present invention comprise from about 0.1%), preferably from about 1%, more preferably from about 5%, most preferably from about 10%) to about 20%, more preferably to about 15%> by weight, of a fragrance delivery system as described herein.
The fragrance delivery system of the present invention is a ternary component system wherein fragrance raw materials are delivered to fabric via three "vectors" or in three ways: a) by way of one or more cyclodextrin inclusion complexes; b) by way of an uncomplexed fragrance raw material admixture; and c) by way of a pro-fragrance.
The following is a description of the components which comprise the fragrance delivery systems of the present invention. Cyclodextrin Complexing Agent
The fragrance delivery system of the present invention comprises from about 50%, preferably from about 55%), more preferably from about 60%>, most preferably from about 65%> to about 99%>, preferably to about 95%>, more preferably to about 90% by weight of a cyclodextrin inclusion complex which comprises one or more fragrance raw materials which are complexed with one or more cyclodextrins. The loading of fragrance raw materials in the cyclodextrin complexes of the present invention is from about 8%> to about 18%.
As used herein, the term "cyclodextrin" (CD) includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-, beta-, gamma-cyclodextrins, and mixtures thereof, and/or their derivatives, and/or mixtures thereof, that are capable of forming inclusion complexes with fragrance raw materials or pro-accords. The specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume. The "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic. The unique shape and physical-chemical properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules such as fragrance raw material molecules which can fit into the cavity. The fragrance raw material/cyclodextrin complex is thus an example of molecular encapsulation.
Beta-cyclodextrin is the most preferred cyclodextrin and the one whose complex benefits most from its affinity to form inclusion complexes. Alpha-, beta-, and gamma- cyclodextrins can be obtained from, among others, Cerestar USA, Inc., Hammond, Indiana and Wacker Chemicals (USA), Inc., New Canaan, Connecticut . There are many derivatives of cyclodextrins that are known. Representative derivatives are those disclosed in U.S. Pat. Nos: 3,426,011, Parmerter et al., issued Feb. 4, 1969; 3,453,257, 3,453,258, 3,453,259, and 3,453,260, all in the names of Parmerter et al., and all issued July 1, 1969; 3,459,731, Gramera et al., issued Aug. 5, 1969; 3,553,191, Parmerter et al., issued Jan. 5, 1971 ; 3,565,887, Parmerter et al., issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13, 1985; 4,616,008, Hirai et al., issued Oct. 7, 1986; 4,638,058, Brandt et al., issued Jan. 20, 1987; 4,746,734, Tsuchiyama et al., issued May 24, 1988; and 4,678,598, Ogino et al., issued July 7, 1987, all of said patents being incorporated herein by reference. Examples of cyclodextrin derivatives suitable for use herein are methyl-β-CD, hydroxyethyl-β-CD, and hydroxypropyl-β-CD of different degrees of substitution (DS), available from, among others, Cerestar USA Inc., Hammond, Indiana, Aldrich Chemical Company, Milwaukee, Wisconsin; Wacker Chemicals (USA), New Canaan, Connecticut; and Chinoin Pharmaceutical Works, Budapest, Hungary. Water-soluble derivatives are also highly desirable.
The individual cyclodextrins can also be linked together, e.g., using multifunctional agents to form oligomers, polymers, etc. Examples of such materials are available commercially from Cerestar USA and from Aldrich Chemical Company (β- CD/epichlorohydrin copolymers).
It is also desirable to use mixtures of cyclodextrins to provide a mixture of complexes. Mixtures of cyclodextrins can conveniently be obtained by using intermediate products from known processes for the preparation of cyclodextrins including those processes described in U.S. 3,425,910, Armbruster et al, issued February 4, 1969; U.S. 3,812,01 1, Okada et al, issued May 21, 1974; U.S. 4,317,881, Yagi et al, issued March 2, 1982; U.S. 4,418,144, Okada et al, issued November 29, 1983; and U.S. 4,738,923, Ammeraal, issued April 19, 1988, all of said patents being incorporated herein by reference. Preferably at least a major portion of the cyclodextrins are alpha-cyclodextrin, beta-cyclodextrin, and/or gamma-cyclodextrin, more preferably beta-cyclodextrin. Some cyclodextrin mixtures are commercially available from, e.g., Ensuiko Sugar Refining Company, Yokohama, Japan.
Fragrance Raw Materials
The fragrance delivery systems of the present invention comprise a fragrance raw material admixture component which comprises one or more fragrance raw materials which are added directly the fabric softener composition. The compositions of the present invention comprise from about 1%>, preferably from about 5%, more preferably from about 20% to about 90%), preferably to about 70%>, more preferably to about 50% by weight, of the fragrance delivery system, a fragrance raw material admixture.
The following describes fragrance raw materials according to the present invention. For the purposes of the present invention "fragrance raw materials" are herein defined as compounds having a molecular weight of at least 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent either alone or in combination with other "fragrance raw materials".
Typically "fragrance raw materials" comprise inter alia alcohols, ketones, aldehydes, esters, ethers, nitriles, and cyclic and acyclic alkenes such as terpenes. A listing of common "fragrance raw materials" can be found in various reference sources, for example, "Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology"; Mϋller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) both incorporated herein by reference.
Non-limiting examples of fragrance raw material alcohols suitable for use as fragrance raw materials of the present invention include 2,4-dimethyl-3-cyclohexene-l-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-l- methylethenylbicyclo[2.2.1]hept-5-ene-2-methanol (Arbozol), 2,4,6-trimethyl-3-cyclohexene-l- methanol (Isocyclo geraniol), 4-(l-methylethyl)cyclohexanemethanol (Mayol), -3,3-trimethyl- 2-norborane methanol, 1,1 -dimethyl- l-(4-methylcyclohex-3-enyl)methanol, 2-phenylethanol, 2- cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p- methylphenyl)ethanol, 6,6-dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanol (nopol), 2-(4- methylphenoxy)ethanol, 3,3-dimethyl-Δ2-β-norbornane ethanol, 2-methyl-2-cyclohexylethanol, l-(4-isopropylcyclohexyl)-ethanol, 1-phenylethanol, l,l-dimethyl-2-phenylethanol, 1,1- dimethyl-2-(4-methyl-phenyl)ethanol, 1 -phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl)propan- 1 -ol (Hydroxy-ambran), 2,2-dimethyl-3-(3- methylphenyl)propan-l-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propen-l-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-l-ol (methylcinnamyl alcohol), α-n-pentyl-3- phenyl-2-propen-l-ol (α-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4- methylphenyl)-2-propanol, 3-(4-methylcyclohex-3-ene)butanol, 2-methyl-4-(2,2,3-trimethyl-3- cyclopenten-l-yl)butanol, 2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-2-buten-l-ol, 3-methyl- 2-buten- 1 -ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten- 1 -yl)-2-buten- 1 -ol, 3-hydroxy-2- butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4-(4- hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, c/s-3-pentenol, 3- methyl-pentanol, 3-methyl-3-penten- 1 -ol, 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl- 5-phenylpentanol (Phenoxanol), 2-methyl-5-phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo- [2.2.1.0(2,6)]hept-3-yl)-2-penten-l-ol (santalol), 4-methyl- 1 -phenyl-2-pentanol, (1-methyl- bicyclo[2.1.1 ]hepten-2-yl)-2-methylpent- 1 -en-3 -ol, 3 -methyl- 1 -phenylpentan-3-ol, 1 ,2- dimethyl-3-( 1 -methylethenyl)cyclopentan- 1 -ol, 2-isopropyl-5-methyl-2-hexenol, c/s-3-hexen- 1 - ol, tra«s-2-hexen-l-ol, 2-isoproenyl-4-methyl-4-hexen- 1 -ol (Lavandulol), 2-ethyl-2-prenyl-3- hexenol, l-hydroxymethyl-4-iso-propenyl-l-cyclohexene (Dihydrocuminyl alcohol), 1-methyl- 4-isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-l-ol, 1-methyl- 4-iso-propenylcyclohexan-3-ol, 4-isopropyl- 1 -methylcyclohexan-3-ol, 4-tert-butylcyclo- hexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 4-isopropyl- cyclohexanol, 4-methyl- 1 -( 1 -methylethyl)-3-cyclohexen- 1 -ol, 2-(5,6,6-trimethyl-2- norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, l-methyI-4- isopropylcyclohexan-3-ol, l,2-dimethyl-3-(l-methylethyl)cyclohexan-l-ol, heptanol, 2,4- dimethylheptan- 1 -ol, 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-2- oxymethylbicyclo[3.1.1]hept-2-ene (myrtenol), 4-methyl-2,4-heptadien-l-ol, 3,4,5,6,6- pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethyl-3-hydroxy-2- methylenebicyclo[3.1.1 ]heptane, 1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-ol, 2,6-dimethylheptan- 2-ol, 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl- 6-methylene-7-octen-2-ol (myrcenol), 7-methyloctan- 1 -ol, 3,7-dimethyl-6-octenol, 3,7- dimethyl-7-octenol, 3,7-dimethyl-6-octen-l-ol (citronellol), 3,7-dimethyl-2,6-octadien-l-ol (geraniol), 3,7-dimethyl-2,6-octadien-l-ol (nerol), 3,7-dimethyl-l,6-octadien-3-ol (linalool), 3,7- dimethyloctan- 1 -ol (pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-l-ol, 3,7-dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-5,7-octadien-2-ol, 4,7- dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan- 3-ol, 3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadien-2-ol (muguol), 3 -methyl- l-octen-3-ol, 7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-l-ol, cis-6-nonen-l-ol, 6,8-dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone, 2-nonen-l-ol, 2,4- nonadien-1-ol, 3,7-dimethyl-l,6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol, 2- decen-1-ol, 2,4-decadien-l-ol, 4-methyl-3-decen-5-ol, 3,7,9-trimethyl-l,6-decadien-3-ol (isobutyl linallol), undecanol, 2-undecen- 1 -ol, 10-undecen-l-ol, 2-dodecen-l-ol, 2,4- dodecadien-1-ol, 2,7,1 l-trimethyl-2,6,10-dodecatrien-l-ol (farnesol), 3,7,11-trimethyl- 1,6, 10,- dodecatrien-3-ol, 3,7,1 l,15-tetramethylhexadec-2-en-l-ol (phytol), 3,7,11,15- tetramethylhexadec-l-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), /?ara-cymen-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl salicylate, cκ-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2- methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4-(l-propenyl)phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2- methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ort&o-hydroxy benzoate, ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy- 1 -methylbenzene, 2-tert-butyl-4-methy 1- 1 -hydroxybenzene, 1 -ethoxy-2-hydroxy-4- propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4- hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3,3- trimethyl-2-norbornanol (fenchol), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano- 1 H- inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-lH-inden-5-ol, 2-methyl-2- vinyl-5-(l-hydroxy-l-methylethyl)tetrahydrofuran, β-caryophyllene alcohol, and mixtures thereof.
Non-limiting examples of fragrance raw material aldehydes suitable for use in the fragrance delivery system according to the present invention include phenylacetaldehyde, p- methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methylnonyl acetaldehyde, phenylpropanal, 3-(4-t-butylphenyl)-2-methyl propanal (Lilial), 3-(4-t-butylphenyl)-propanal (Bourgeonal), 3-(4-methoxyphenyl)-2-methylpropanal (Canthoxal), 3-(4-isopropylphenyl)-2- methylpropanal (Cymal), 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (Helional), 3-(4- ethylpheny)-2,2-dimethylpropanal (Floralozone), phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, traws-2-hexenal, cw-hex-3-enal, heptanal, cw-4-heptenal, 2-ethyl-2-heptenal, 2,6- dimethyl-5-heptenal (Melonal), 2,4-heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal, 3,7- dimethyl-2,6-octadien-l-al, 3,7-dimethyl-l,6-octadien-3-al, 3,7-dimethyl-6-octenal (citronellal), 3,7-dimethyl-7-hydroxyoctan-l-al (hydroxy citronellal), nonanal, 6-nonenal, 2,4-nonadienal, 2,6-nonadienal, decanal, 2-methyl decanal, 4-decenal, 9-decenal, 2,4-decadienal, undecanal, 2- methyldecanal, 2-methylundecanal, 2,6, 10-trimethyl-9-undecenal (Adoxal), undec- 10-enyl aldehyde, undec-8-enanal, dodecanal, tridecanal, tetradecanal, anisaldehyde, bourgenonal, cinnamic aldehyde, α-amylcinnam-aldehyde, α-hexyl cinnamaldehyde, methoxy- cinnamaldehyde, isocyclocitral, citronellyl oxyacet-aldehyde, cortexaldehyde, cumminic aldehyde, cyclamen aldehyde, florhydral, heliotropin, hydrotropic aldehyde, vanillin, ethyl vanillin, benzaldehyde, p-methyl benzaldehyde, 3,4-dimethoxybenzaldehyde, 3- and 4-(4- hydroxy-4-methyl-pentyl)-3-cyclohexene- 1 -carboxaldehyde (Lyral), 2,4-dimethyl-3- cyclohexene-1-carboxaldehyde (Triplal), l-methyl-3-(4-methylpentyl)-3- cyclohexencarboxaldehyde (Vernaldehyde), p-methylphenoxyacetaldehyde (Xi aldehyde), and mixtures thereof.
Non-limiting examples of fragrance raw material ketones suitable for use in the fragrance delivery systems according to the present invention include -damascone, β- damascone, δ-damascone, β-damascenone, muscone, 6,7-dihydro-l,l,2,3,3-pentamethyl-4(5H)- indanone (cashmeran), c/s-jasmone, dihydrojasmone, α-ionone, β-ionone, dihydro-β-ionone, γ- methyl ionone, -wo-methyl ionone, 4-(3,4-methylenedioxyphenyl)butan-2-one, 4-(4- hydroxyphenyl)butan-2-one, methyl β-naphthyl ketone, methyl cedryl ketone, 6-acetyl- 1,1,2,4,4,7-hexamethyltetralin (tonalid), /-carvone, 5-cyclohexadecen-l-one, acetophenone, decatone, 2-[2-(4-methyl-3-cyclohexenyl-l-yl)propyl]cyclopentan-2-one, 2-sec- butylcyclohexanone, β-dihydro ionone, allyl ionone, α-irone, α-cetone, α-irisone, acetanisole, geranyl acetone, l-(2-methyl-5-isopropyl-2-cyclohexenyl)-l-propanone, acetyl diisoamylene, methyl cyclocitrone, 4-t-pentyl cyclohexanone, p-t-butylcyclohexanone, o-t- butylcyclohexanone, ethyl amyl ketone, ethyl pentyl ketone, menthone, methyl-7,3-dihydro-2H- l,5-benzodioxepine-3-one, fenchone, and mixtures thereof.
Non-limiting examples of fragrance raw material esters suitable for use in the fragrance delivery systems according to the present invention include geranyl formate, citronellyl formate, phenylethyl formate, phenoxyethyl formate, trα«s-2-hexenyl formate, c/s-3-hexenyl formate, cw-6-nonenyl formate, 9-decenyl formate, 3,5,5-trimethylhexyl formate, 3-methyl-5- phenylpentanyl formate, 6-methylheptan-2-yl formate, 4-(2,2,6-trimethyl-2-cyclohexen-l-yl)-3- buten-2-yl formate, 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-l-yl)-4-penten-2-yl formate, 4- isopropylcyclohexyleth-2-yl formate, 6,8-dimethylnonan-2-yl formate, decahydro- β-naphthyl formate, 4-isopropylcyclohexylmethyl formate, linalyl formate, lavandulyl formate, citronellyl formate, α-terpinyl formate, nopyl formate, isobornyl formate, bornyl formate, isobornyl formate, guaiyl formate, 2-tert-butylyclohexyl formate, 4-tert-butylcyclohexyl formate, decahydro- β-naphthyl formate, menthyl formate, p-menthanyl formate, neryl formate, cinnamyl formate, ethyl acetate, butyl acetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethylhexyl acetate, geranyl acetate, citronellyl acetate, phenylethyl acetate, phenoxyethyl acetate, trans-2-hexenyl acetate, cw-3-hexenyl acetate, s-6-nonenyl acetate, 9-decenyl acetate, 3-methyl-5- phenylpentanyl acetate, 6-methyl-heptan-2-yl acetate, 4-(2,2,6-trimethyl-2-cyclohexen-l-yl)-3- buten-2-yl acetate, 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-l-yl)-4-penten-2-yl acetate, decahydro- β-naphthyl acetate, menthyl acetate, benzyl acetate, 4-isopropylcyclohexyleth-2-yl acetate, 6,8-dimethylnonan-2-yl acetate, 1 -phenylethyl acetate, 4-isoproylcyclo-hexylmethyl acetate, linalyl acetate, lavandulyl acetate, citronellyl acetate, α-terpinyl acetate, nopyl acetate, isobornyl acetate, bornyl acetate, isobornyl acetate, guaiyl acetate, 2-tert-butylyclohexyl acetate, 4-tert-butylcyclohexyl acetate, decahydro- β-naphthyl acetate, menthyl acetate, p-menthanyl acetate, neryl acetate, cinnamyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, c/s-3-hexenyl butyrate, cw-3-hexenyl isobutyrate, ethyl isovalerate, 2- methylbutyrate, ethyl hexanoate, 2-propenyl hexanoate, ethyl heptanoate, 2-propenyl heptanoate, ethyl octanoate, ethyl 2-trøws-4-cw-decadienoate, methyl 2-nonynoate, benzyl propionate, benzyl isovalerate, phenylethyl isobutyrate, phenylethyl isovalerate, α,α-dimethyl phenylethyl butyrate, methyl benzoate, hexyl benzoate, benzyl benzoate, ethyl phenylacetate, geranyl phenylacetate, 1 -phenylethyl phenylacetate, methyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, geranyl propionate, geranyl isobutyrate, geranyl isovalerate, linalyl propionate, linalyl buryrate, linalyl isobutyrate, citronellyl propionate, citronellyl isobutyrate, citronellyl isovalerate, citronellyl tiglate, allyl 3-cyclohexylpropionate, methyl dihydrojasmonate, methyl 2-hexyl-3-oxocyclopentane-carboxylate, and mixtures thereof. Pro- fragrances
The fragrance delivery systems according to the present invention comprise from about 1%), preferably from about 2% to about 50%, preferably to about 25% by weight, of one or more β-ketoesters pro- fragrances having the formula:
Figure imgf000011_0001
wherein R is alkoxy derived from a fragrance raw material alcohol. Non-limiting examples of preferred fragrance raw material alcohols are described herein above. Most preferred alcohols which are delivered via a β-ketoester pro-fragrance are linalool, dihydromyrcenol, and mixtures thereof.
Rl, R and R^ are each independently hydrogen, C]-C3ø substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, Cg-C3Q substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R* , R^, or R3 is a unit having the formula:
Figure imgf000012_0001
wherein R^, R5, and R^ are each independently hydrogen, C1 -C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1 -C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy,
C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C5-C30 substituted or unsubstituted aryl; or R % R->, and R" can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof.
Preferably at least two R*, R or R^ units are hydrogen. In one embodiment of the present invention preferably R % R- and R" units are each hydrogen. In addition, preferably when two R^, R$, and R" units are hydrogen, the remaining unit is C1 -C20 substituted or unsubstituted linear alkyl, C3-C20 substituted or unsubstituted branched alkyl, C3-C20 substituted or unsubstituted cyclic alkyl; more preferably methyl. Also preferably R^, R-\ and
R" are taken together to form a C6-C30 substituted or unsubstituted aryl unit, preferably substituted or unsubstituted phenyl and naphthyl. For the purposes of the present invention the term "substituted" as it applies to linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl, branched alkenyl, cyclic alkenyl, branched alkoxy, cyclic alkoxy, alkynyl, and branched alkynyl units are defined as "carbon chains which comprise substitutents other than branching of the carbon atom chain", for example, other than the branching of alkyl units (e.g. isopropyl, isobutyl). Non-limiting examples of "substituents" include hydroxy, C1 -C12 alkoxy, preferably methoxy; C3-C12 branched alkoxy, preferably isopropoxy; C3-C12 cyclic alkoxy; nitrilo; halogen, preferably chloro and bro o, more preferably chloro; nitro; morpholino; cyano; carboxyl, non-limiting examples of which are - CHO; -C02-M+, -C02R9; -CONH2; -CONHR9; -CONR9 2; wherein R9 is Cι -C12 linear or branched alkyl); -S03 " M+; -OSO3- M+; -N(R10) ; and -N+(R10)3χ- wherein each R10 is independently hydrogen or C1 -C4 alkyl; and mixtures thereof; wherein M is hydrogen or a water soluble cation; and X is chlorine, bromine, iodine, or other water soluble anion.
The preferred pro-fragrance according to the present invention is 3,7-dimethyl-l,6- octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate which delivers the fragrance raw material alcohol linalool.
OTHER INGREDIENTS Fabric Softening Actives
The compositions of the present invention comprise at least about 1%>, preferably from about 10%), more preferably from about 20% to about 80%>, more preferably to about 60%> by weight, of the composition of one or more fabric softener actives.
The preferred fabric softening actives according to the present invention are amines having the formula:
Figure imgf000013_0001
quaternary ammonium compounds having the formula:
+
(R)- -N- (CH2)n-Q-R] X "
4-m
and mixtures thereof, wherein each R is independently Ci -Cg alkyl, Ci -Cg hydroxyalkyl, benzyl, and mixtures thereof; R^ is preferably C1 1 -C22 linear alkyl, C] i -C22 branched alkyl, C] i -C22 linear alkenyl, C1 1-C22 branched alkenyl, and mixtures thereof; Q is a carbonyl moiety independently selected from the units having the formula: 0 0 R2 0 0 R2
II II o— C- — c— o— - , — N- -c- - , — C-N- O
0 R3 0 0— C— R1 O
II 1 II 1 II o— C- -o — — CH- -o— c — -CH-CH2-0— C wherein R^ is hydrogen, C1 -C4 alkyl, preferably hydrogen; R^ is CJ-C4 alkyl, preferably hydrogen or methyl; preferably Q has the formula:
O O
II II
— O— C or — NH-C •
X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate. The anion can also, but less preferably, carry a double charge, in which case X'") represents half a group. The index m has a value of from 1 to 3; the index n has a value of from 1 to 4, preferably 2 or 3, more preferably 2.
One embodiment of the present invention provides for amines and quaternized amines having two or more different values for the index n per molecule, for example, a softener active prepared from the starting amine methyl(3-aminopropyl)(2-hydroxyethyl)amine.
More preferred softener actives according to the present invention have the formula:
O
+
(R) -N- -(CH2)n-0— C— R1 X
4-m
wherein the unit having the formula:
O
— O— C— R1 is a fatty acyl moiety. Suitable fatty acyl moieties for use in the softener actives of the present invention are derived from sources of triglycerides including tallow, vegetable oils and/or partially hydrogenated vegetable oils including inter alia canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil. Yet more preferred are the Diester Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2. The R! units are typically mixtures of linear and branched chains of both saturated and unsaturated aliphatic fatty acids, an example of which (canola oil), is described in Table I herein below.
Table I
Figure imgf000015_0001
The formulator, depending upon the desired physical and performance properties of the final fabric softener active, can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of triglyceride to form a "customized blend". However, those skilled in the art of fats and oils recognize that the fatty acyl composition may vary, as in the case of vegetable oil, from crop to crop, or from variety of vegetable oil source to variety of vegetable oil source. DEQA's which are prepared using fatty acids derived from natural sources are preferred.
A preferred embodiment of the present invention provides softener actives comprising R units which have at least about 3%>, preferably at least about 5%, more preferably at least about 10%), most preferably at least about 15%> C1 1-C22 alkenyl, including polyalkenyl (polyunsaturated) units wter alia oleic, linoleic, linolenic.
For the purposes of the present invention the term "mixed chain fatty acyl units" is defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains having from 10 carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case of alkenyl chains, from one to three double bonds, preferably all double bonds in the cis configuration". With regard to the R* units of the present invention, it is preferred that at least a substantial percentage of the fatty acyl groups are unsaturated, e.g., from about 25%), preferably from about 50%) to about 70%), preferably to about 65%. The total level of fabric softening active containing polyunsaturated fatty acyl groups can be from about 3%, preferably from about 5%, more preferably from about 10% to about 30%>, preferably to about 25%, more preferably to about 18%>. As stated herein above cis and trans isomers can be used, preferably with a cisltrans ratio is of from 1 :1, preferably at least 3:1, and more preferably from about 4:1 to about 50: 1, more preferably about 20: 1, however, the minimum being 1 : 1.
The level of unsaturation contained within the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
Indeed, for compounds having the formula:
+
(R) -N- (CH2)n-Q-R] X
4:-m
derived from tallow fatty acids, when the Iodine Value is from 5 to 25, preferably 15 to 20, it has been found that a cisltrans isomer weight ratio greater than about 30/70, preferably greater than about 50/50 and more preferably greater than about 70/30 provides optimal concentrability.
For compounds of this type made from tallow fatty acids having a Iodine Value of above 25, the ratio of cis to trans isomers has been found to be less critical unless very high concentrations are needed. A further preferred embodiment of the present invention comprises DEQA's wherein the average Iodine Value for R^ is approximately 45.
The R! units suitable for use in the isotropic liquids present invention can be further characterized in that the Iodine Value (IV) of the parent fatty acid, said IV is preferably from about 10, more preferably from about 50, most preferably from about 70, to a value of about 140, preferably to about 130, more preferably to about 115. However, formulators, depending upon which embodiment of the present invention they choose to execute, may wish to add an amount of fatty acyl units which have Iodine Values outside the range listed herein above. For example, "hardened stock" (IV less than or equal to about 10) may be combined with the source of fatty acid admixture to adjust the properties of the final softener active.
A prefered source of fatty acyl units, especially fatty acyl units having branching, for example, "Guerbet branching", methyl, ethyl, etc. units substituted along the primary alkyl chain, synthetic sources of fatty acyl units are also suitable. For example, the formulator may with to add one or more fatty acyl units having a methyl branch at a "non-naturally occuring" position, for example, at the third carbon of a C17 chain. What is meant herein by the term "non-naturally occuring" is "acyl units whihc are not found in significant (greater than about 0.1%) quantities is common fats and oils which serve as feedstocks for the source of triglycerides described herein." If the desired branched chain fatty acyl unit is unavailable from readily available natural feedstocks, therefore, synthetic fatty acid can be suitably admixed with other synthetic materials or with other natural triglyceride derived sources of acyl units.
The following are examples of preferred softener actives according to the present invention.
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;
N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tri(canolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride; l,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1 ,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride; and mixtures of the above actives. Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy-ethyl)-N,N- dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
Additional fabric softening agents useful herein are described in U.S. 5,643,865 Mermelstein et al, issued July 1, 1997; U.S. 5,622,925 de Buzzaccarini et al, issued April 22, 1997; U.S. 5,545,350 Baker et al, issued August 13, 1996; U.S. 5,474,690 Wahl et al, issued December 12, 1995; U.S. 5,417,868 Turner et al, issued January 27, 1994; U.S. 4,661,269 Trinh et al, issued April 28, 1987; U.S. 4,439,335 Burns, issued March 27, 1984; U.S. 4,401,578 Verbruggen, issued August 30, 1983; U.S. 4,308,151 Cambre, issued December 29, 1981; U.S. 4,237,016 Rudkin et al, issued October 27, 1978; U.S. 4,233,164 Davis, issued November 11, 1980; U.S. 4,045,361 Watt et al, issued August 30, 1977; U.S. 3,974,076 Wiersema et al, issued August 10, 1976; U.S. 3,886,075 Bernadino, issued May 6, 1975; U.S. 3,861,870 Edwards et al, issued January 21 1975; and European Patent Application publication No. 472,178, by Yamamura et al., all of said documents being incorporated herein by reference. Color Care Agents
The compositions of the present invention preferably comprise a color care agent. When used, the composition comprises from about 0.01%, preferably from about 0.1%o, more preferably from about 0.5%) to about 20%, more preferably to about 10%>, most preferably to about 7% by weight, of a color care agent.
Preferred color care agents have the formula:
(R')(R2)N(CX2)nN(R3)(R4) wherein R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen; C,-C10 linear or branched alkyl; CrC10 linear or branched alkenyl; C,-C10 linear or branched alkyl which is substituted by one or more hydroxyl units; C,-C10 linear or branched alkenyl which is substituted by one or more hydroxyl units; an alkyleneoxy unit having the formula: (R5OMR60)yR7 wherein R5 is 1,2-propylene, 1,3-propylene, 1 ,4-butylene, and mixtures thereof, R6 is ethylene, R7 is hydrogen, CrC10 linear or branched alkyl, and mixtures thereof, x is an integer form 0 to 50, y is an integer from 0 to 50; alkyleneamine units having the formula:
— (CX2)nN(R8)(R9)
wherein R8 and R9 are each independently selected from the units which comprise R1. Preferred R1, R2, R3, and R4 are hydrogen, 2-hydroxypropyl, alkyleneoxy units, alkyleneamine units and mixtures thereof. A prefered color care agent is N,N,N',N'-tetrakis-(2- hydroxypropyl)ethylenediamine. In addition, compositions wherein R1, R2, R3, and R4 comprise at least one -CH2CH2CH2N(H)(R60)yH unit wherein y is from 1-5, and the balance of said moieties are hydrogen, are prefered.
X is hydrogen, hydroxy, C,-C10 linear or branched alkyl, and mixtures thereof, preferably hydrogen. The index n is an integer from 1 to 6.
ADJUNCT INGREDIENTS The compositions of the present invention may also optionally comprise one or more adjunct ingredients. Non-limiting examples of adjunct ingredients are selected from the group consisting of chelating agents, cationic charge boosters, dispersibility aids, soil release agents, nonionic fabric softening agents, preservatives, colorants, optical brighteners, opacifiers, anti- shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, and mixtures thereof.
SUBSTRATE ARTICLES
One aspect of the present invention relates to fabric enhancement compositions which are delivered to fabric via dryer-added substrate. In preferred embodiments of substrate delivered compositions, the present invention encompasses articles of manufacture. Representative articles are those that are adapted to soften fabrics in an automatic laundry dryer, of the types disclosed in U.S. Patent 3,989,631, Marsan, issued Nov. 2, 1976; U.S. Patent 4,055,248, Marsan, issued Oct. 25, 1977; U.S. Patent 4,073,996, Bedenk et al., issued Feb. 14, 1978; U.S. Patent 4,022,938, Zaki et al., issued May 10, 1977; U.S. Patent 4,764,289, Trinh, issued Aug. 16, 1988; U.S. Patent 4,808,086, Evans et al., issued Feb. 28,1989; U.S. Patent 4,000,340, Murphy et al., issued Dec. 28, 1976; U.S. Patent 4,103,047, Zaki et al., issued July 25, 1978; U. S. Patent 3,736,668, Dillarstone, issued June 5, 1973; U. S. Patent 3,701,202, Compa et al., issued October 31, 1972; U. S. Patent 3,634,947, Furgal, issued January 18, 1972; U. S. Patent 3,633,538, Hoeflin, issued January 11, 1972; U. S. Patent 3,435,537, Ru sey, issued April 1, 1969; all of which are incorporated herein by reference.
In a preferred substrate article embodiment, the fabric treatment compositions are provided as an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer. Such dispensing means can be designed for single usage or for multiple uses. The dispensing means can also be a "material" that releases the fabric softener composition and then is dispersed and/or exhausted from the dryer.
A highly preferred article herein comprises the fabric treatment composition releasably affixed to a flexible substrate in a sheet configuration. Highly preferred paper, woven or nonwoven "absorbent" substrates useful herein are fully disclosed in U. S. Patent 3,686,025, Morton, issued August 22, 1972, incorporated herein by reference. It is known that most substances are able to absorb a liquid substance to some degree; however, the term "absorbent" as used herein, is intended to mean a substance with an absorbent capacity (i.e., a parameter representing a substrate's ability to take up and retain a liquid) from 4 to 12, preferably, 5 to 7, times its weight of water.
Determination of absorbent capacity values is made by using the capacity testing procedures described in U. S. Federal Specification UU-T-595b, modified as follows:
1. tap water is used instead of distilled water;
2. the specimen in immersed for 30 seconds instead of 3 minutes;
3. draining time is 15 seconds instead of 1 minute; and
4. the specimen is immediately weighed on a torsion balance having a pan with turned-up edges.
Absorbent capacity values are then calculated in accordance with the formula given in said Specification. Based on this test, one-ply, dense bleached paper (e.g., kraft or bond having a basis eight of about 32 pounds per 3,000 square feet) has an absorbent capacity of 3.5 to 4, commercially available household one-ply toweling paper has a value of 5 to 6; and commercially available two-ply household toweling paper has a value of 7 to about 9.5.
Using a substrate with an absorbent capacity of less than 4 tends to cause too rapid release of the fabric treatment composition from the substrate resulting in several disadvantages, one of which is uneven conditioning of the fabrics. Using a substrate with an absorbent capacity over 12 is undesirable, inasmuch as too little of the fabric treatment composition is released to condition the fabrics in optimal fashion during a normal drying cycle.
Such a substrate comprises a nonwoven cloth having an absorbent capacity of preferably from about 5 to 7 and wherein the weight ratio of fabric treatment composition to substrate on a dry weight basis ranges from about 5:1 to 1 : 1.
Non-woven cloth substrate preferably comprises cellulosic fibers having a length of from 3/16 inch to 2 inches a denier of from 1.5 to 5 and the substrate is adhesively bonded together with a binder resin.
The flexible substrate preferably has openings sufficient in size and number to reduce restriction by said article of the flow of air through an automatic laundry dryer. The better openings comprise a plurality of rectilinear slits extended along one dimension of the substrate.
Use of the Article of Manufacture The dispensing means will normally carry an effective amount of fabric treatment composition. Such effective amount typically provides sufficient fabric conditioning agent and or anionic polymeric soil release agent for at least one treatment of a minimum load in an automatic laundry dryer. Amounts of fabric treatment composition for multiple uses, e.g., up to about 30, can be used. Typical amounts for a single article can vary from about 0.25g to about 100 gm.
One such article comprises sponge material releasably enclosing enough fabric treatment composition to effectively impart fabric soil release and softness benefits during several cycles of clothes. This multi-use article can be made by filling a hollow sponge with about 20 gms of the fabric treatment composition.
The substrate embodiment of this invention can be used for imparting the above- described fabric treatment composition to fabric to provide softening and/or antistatic effects together with color fidelity benefits to fabric in an automatic laundry dryer. Generally, the method of using the composition of the present invention comprises: commingling pieces of damp fabric by tumbling said fabric under heat in an automatic clothes dryer with an effective amount of the fabric treatment composition.
METHOD OF USE The present invention also relates to a method for using the fragrance delivery system of the present invention to provide fabric with enhanced fragrance longevity benefits delivered via the automatic dryer. The method comprises the step of contacting clothing in an automatic dryer with an article of manufacture which comprises:
A) a substrate in the form of a sheet; and
B) a fabric conditioning composition, said composition disposed on said sheet, and said composition comprising: a) from about 1% to about 80% by weight, of a fabric softening active; b) from about 0.1 % by weight, of a fragrance delivery system, said fragrance delivery system comprising: i) from about 1%> to about 50%> by weight, of 3,7-dimethyl-l,6- octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate; ii) from about 50% to about 99%> by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from about 8%> to about 18% by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from about 1%> to about 90% by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; iv) the balance carriers; c) from about 0.01% by weight, of a fabric color care agent; and d) the balance carriers and adjunct ingredients.
The following is a procedure for preparing the preferred β-ketoester pro-fragrance component of the present invention, 3,7-dimethyl-l,6-octadien-3-yl 3-(β-naphthyl)-3-oxo- propionate.
Lithium diisopropylamide (101.0 mL of a 2.0 M solution, 0.202 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. 3,7-Dimethyl- l,6-octadien-3-yl acetate (linalyl acetate) in the amount of (18.66 g, 0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of (17.43 g, 0.090 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20 °C and stirred at that temperature for 18 h. After warming to 0 °C, the mixture is quenched with 20%> HCl (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCθ3 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgSθ4 and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and GC analysis and the structure confirmed by mass spectrometry, Η and 13C NMR.
The following compositions illustrate the fabric conditioning compositions which are then deposed upon a substrate material.
TABLE I
Weight % Ingredients 1 2 3 4
Figure imgf000023_0001
1. N,N-di(canolyloxyethyl)-N,N-dimethyl ammonium methyl sulfate.
2. N,N-di(canolyloxyethyl)-N-(2-hydroxyethyl)-N-methyl ammonium methyl sulfate.
3. Stearyl dimethylamine fatty acid salt.
4. N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.
5. Total Percentage of all perfume ingredients.
6. 3 ,7-dimethy 1- 1 ,6-octadien-3 -yl 3 -( β-naphthy l)-3 -oxo-propionate .
7. Includes water, dye, acid, preservatives, etc.

Claims

What is claimed is:
1. A dryer-added fabric conditioning composition comprising:
A) a substrate in the form of a sheet; and
B) a fabric conditioning composition, said composition disposed on said sheet, and said composition comprising: a) from 1% to 80% by weight, of a fabric softening active; b) from 0.1%> by weight, of a fragrance delivery system, said fragrance delivery system comprising: i) from 1% to 50% by weight, of a ╬▓-ketoester pro-fragrance; ii) from 50% to 99% by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from 8% to 18% by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from 1% to 90% by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; iv) the balance carriers; c) from 0.01% by weight, of a fabric color care agent; and d) the balance carriers and adjunct ingredients.
2. A composition according to Claim 1 wherein said fabric softening active comprises a quaternary ammonium compound having the formula:
+
(R) 4-m -N- -(CH2)n-Q-Rl X m or amine precursor having the formula:
Figure imgf000024_0001
wherein each R is independently Ci-Cg alkyl, Ci-C╬▓ hydroxyalkyl, benzyl, and mixtures thereof; R* is C1-C22 alkyl, C3-C22 alkenyl, and mixtures thereof; Q is a carbonyl moiety having the formula:
Figure imgf000025_0001
wherein R^ is hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and mixtures thereof; R^ is hydrogen, C1-C4 alkyl, and mixtures thereof; X is a softener compatible anion; m is from
1 to 3; n is from 1 to 4.
3. A composition according to either Claims 1 or 2 wherein Q has the formula:
O O
II II
ΓÇö OΓÇö C ΓÇö or ΓÇö CΓÇö O ΓÇö
4. A composition according to any of Claims 1-3 wherein R is methyl, hydroxyethyl, and mixtures thereof.
5. A composition according to any of Claims 1-4 wherein n is equal to 2.
6. A composition according to any of Claims 1-5 wherein said quaternary ammonium fabric softening active comprises an acyl moiety having the formula:
O
II — C— R wherein said acyl unit is derived from a source of triglyceride selected from the group consisting of tallow, hard tallow, lard, canola oil, partially hydrogenated canola oil, safflower oil, partially hydrogenated safϊlower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil, partially hydrogenated sunflower oil, com oil, partially hydrogenated com oil, soybean oil, partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil, rice bran oil, partially hydrogenated rice bran oil, synthetic triglyceride feedstocks, and mixtures thereof.
7 A composition according to Claim 1 wherein the fabric softener active is selected from the group consisting of N,N-cU(tallowyl-oxy-emyl)-N,N-climethyl ammonium chloride; N,N- di(canolyloxyethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N- methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-di(canolyloxyethyl)-N-methyl- N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.
8. A composition according to any of Claims 1-7 wherein said ╬▓-ketoester has the formula:
Figure imgf000026_0001
wherein R is alkoxy derived from a fragrance raw material alcohol; R , R^, and R^ are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg- C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R1, R2, or R-> is a unit having the formula:
Figure imgf000026_0002
wherein R% R* ? and R" are each independently hydrogen, C1-C3Q substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl; or R^, R5, and R can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof
9. A composition according to any of Claims 1-8 wherein Rl has the formula:
Figure imgf000027_0001
R^, R3, R4 and R^ are each hydrogen; and R^ is hydrogen, Ci-Cig substituted or unsubstituted linear alkyl, C3-C16 substituted or unsubstituted branched alkyl, and mixtures thereof.
10. A composition according to any of Claims 1-9 wherein Rl has the formula:
Figure imgf000027_0002
R2 and R^ are each hydrogen, R^, R5 and R^ are taken together to form C6-C30 substituted or unsubstituted phenyl, naphthyl, and mixtures thereof.
11. A composition according to any of Claims 1-10 wherein said ╬▓-ketoester is selected from the group consisting of 3,7-dimethyl-l,6-octadien-3-yl 3-(╬▓-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2- yl 3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(╬▓-naphthyl)-3-oxo- propionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, (╬▒,╬▒-4- trimethyl-3-cyclohexenyl)methyl 3-(╬▓-naphthyl)-3-oxo-propionate, 3,7-dimethyl-l,6- octadien-3-yl 3-(╬▒-naphthyl)-3-oxo-propionate, cis 3-hexen-l-yl 3-(╬▓-naphthyl)-3-oxo- propionate, 9-decen-l-yl 3-(╬▓-naphthyl)-3-oxo-propionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-l,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-(╬▓-naphthyl)-3-oxo-2-methylpropionate, 3 ,7-dimethyl- 1,6- octadien-3-yl 3-(╬▓-naphthyl)-3-oxo-2,2-dimethylpropionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(╬▓-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(╬▓-naphthyl)-3- oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof.
12. A dryer-added fabric conditioning composition comprising:
A) a substrate in the form of a sheet; and
B) a fabric conditioning composition, said composition disposed on said sheet, and said composition comprising: a) from 40% to 50% by weight, of a fabric softening active, said fabric softening active having the formula:
Figure imgf000028_0001
wherein R is methyl, R1 is an alkyl moiety derived from a triglyceride source selected from the group consisting of canola oil, safflower oil, peanut oil, sunflower oil, com oil, soybean oil, tall oil, rice bran oil, and mixtures thereof; b) from 5% to 20% by weight, of a fragrance delivery system, said fragrance delivery system comprising: i) from 1% to 7% by weight, of 3,7-<iimethyl-l,6-octadien-3-yl 3-(╬▓- naphthyl)-3-oxo-propionate; ii) from 70% to 85% by weight, of a cyclodextrin inclusion complex delivered fragrance raw material admixture, said inclusion complex comprising: a) from 8% to 18% by weight of a fragrance raw material admixture; b) the balance one or more cyclodextrins; iii) from 10% to 25% by weight, of a fragrance raw material admixture comprising one or more fragrance raw materials; iv) the balance carriers; c) from 1% to 5% by weight, of N,N,N',N'-tetrakis(2- hydroxypropyl)ethylenediamine; and d) the balance carriers and adjunct ingredients.
PCT/US1999/019207 1998-08-25 1999-08-24 Dryer-added fabric softener compositions comprising a ternary fragrance delivery system WO2000011134A1 (en)

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WO2002090480A1 (en) * 2001-05-04 2002-11-14 The Procter & Gamble Company Dryer-added fabric softening articles and methods
US8592361B2 (en) 2002-11-25 2013-11-26 Colgate-Palmolive Company Functional fragrance precursor
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WO2001090285A1 (en) * 2000-05-24 2001-11-29 The Procter & Gamble Company A fabric softening composition comprising a malodor controlling agent
US6794356B2 (en) 2000-05-24 2004-09-21 The Procter & Gamble Company Fabric softening composition comprising a malodor controlling agent
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US6787510B2 (en) 2001-05-04 2004-09-07 The Procter & Gamble Company Dryer-added fabric softening articles and methods
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US8895496B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
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