WO1998047996A1 - Compositions de detergents a lessive renfermant des composes diffuseurs de parfum - Google Patents

Compositions de detergents a lessive renfermant des composes diffuseurs de parfum Download PDF

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Publication number
WO1998047996A1
WO1998047996A1 PCT/US1998/007935 US9807935W WO9847996A1 WO 1998047996 A1 WO1998047996 A1 WO 1998047996A1 US 9807935 W US9807935 W US 9807935W WO 9847996 A1 WO9847996 A1 WO 9847996A1
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substituted
pro
methyl
unsubstituted
fragrance
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PCT/US1998/007935
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English (en)
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Joseph Paul Morelli
Scott William Waite
Eugene Paul Gosselink
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The Procter & Gamble Company
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Publication of WO1998047996A1 publication Critical patent/WO1998047996A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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 laundry detergent compositions which provide a "freshness” or “clean” scent to fabric.
  • the compositions described herein deliver pro-accords to the fabric during laundering.
  • the pro-accords then release fragrance raw materials which provide the fabric with a pleasing, fresh-like odor.
  • the present invention also relates a method for delivering a pleasurable scent to fabric which has a lasting freshness quality.
  • laundry detergent formulators In addition to the removal of stains, dirt, soil, grime, and grease from fabric, laundry detergent formulators have attempted to deliver a "fresh” or “clean” odor to washed clothing to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective.
  • Laundry detergent compositions including rinse-added fabric softeners and dryer-added substrates, are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer but which fail to deliver a prolonged "fragrance” or “pleasurable smell” to the finished, cleaned fabric.
  • fragrance materials are the perfume "top” and “middle” notes which are highly volatile compounds and which are usually detectable at low levels.
  • these highly volatile materials are typically lost either during the prolonged heating which takes place in an automatic dryer or they lack the substantivity necessary to deposit onto the fabric surface and are therefore lost during the laundry rinsing process.
  • the present invention meets the aforementioned needs in that it has been surprisingly discovered that perfume or fragrance accords can be delivered onto fabric "through the wash” from a single precursor pro-accord molecule having high fabric substantivity and that these pro-accords impart a "fresh” or “clean” aesthetic odor benefit to the fabric.
  • the pro-accords according to the present invention continue to release their fragrance raw materials for as long as several weeks depending upon the structure of the pro- accord.
  • the pro-accords described herein comprise fragrance raw materials in a stable, releasable form.
  • the pro-accord containing laundry detergent compositions of the present invention can comprise any number of pro-accords which when taken together are capable of releasing complex perfume fragrances.
  • the pro- accords of the present invention are suitable for delivery of any type of fragrance "characteristic" desired by the formulator.
  • the first aspect of the present invention relates to laundry detergent compositions which provide fabric with enhanced fragrance longevity, comprising: a) at least about 0.01 %, preferably from about 0.01 % to about 10%, more preferably from about 0.1% to about 1% by weight, of a fragrance delivery system comprising one or more pro-accords, said pro-accords formed from at least one fragrance raw material and capable of releasing two or more fragrance raw materials wherein provided said pro-accord: i) comprises fragrance raw materials having a molecular weight greater than or equal to about 100 g/mol; ii) has a molecular weight greater than or equal to about 300 g/mol; iii) has a molecular weight at least two times greater than the lowest molecular weight fragrance raw material which comprises said pro-accord; and iv) has a fragrance release half-life of less than about 1 hour when measured in a 90:10 dioxane/1 N HC1 mixture at pH 0, preferably a fragrance release half-life of less than about 12 hours when measured in NaH
  • a further aspect of the present invention relates to methods for selecting a suitable pro-accord for use in providing a fragrance benefit to fabric wherein the fragrance has enhanced odor longevity.
  • a yet further aspect of the present invention relates to methods for providing an extended "fresh" and “clean” odor benefit to fabric comprising the step of laundering fabric in an aqueous solution of a laundry detergent composition comprising one or more pro-accords described herein.
  • the laundry detergent compositions of the present invention comprise a fragrance delivery system which lays down one or more fragrance "pro-accord” compounds onto the fabric surface during the laundry wash cycle. Because the pro- accords of the present invention generally have a higher molecular weight than uncombined fragrance raw materials and other "pro-fragrance-type" compounds (i.e. those pro-fragrances which only deliver a single equivalent of a fragrance raw material), the pro-accords of the present invention are a means for effectively delivering two or more fragrance raw materials to the fabric surface even upon exposure to prolonged heating which occurs during automatic dryer usage.
  • pro-accords begins to release the fragrance or perfume accord and because this release of material is protracted, the fabric remains “fresh” and “clean” smelling longer.
  • pro-accords according to the present invention can also be designed to be “heat activated” so as to release a "freshening scent” to the fabric during drying. Therefore, heat-activated pro-accords can be delivered to the fabric surface. This results in a fabric having high “initial scent” as well as the lower “clean” and “fresh” scent obtained by the protracted release of non-activated accords.
  • heat activated pro- accords are compounds which have a higher release rate of their fragrance materials after exposure to elevated temperatures. Therefore the formulator may achieve an initial high fragrance delivery coupled with the longer term sustained release.
  • the pro-accords of the present invention are therefore a means for delivering two or more fragrance raw materials onto fabric and thereby providing the fabric with a longer and more sustained "fresh” or “clean” smell.
  • These mixtures of two or more released fragrance raw materials are known by those skilled in the art of fragrances and perfumes as “accords”, thus the term “pro-accord” is used to describe the compounds which comprise the fragrance delivery system of the present invention.
  • the term “accord” as used herein is defined as "mixtures of two or more 'fragrance raw materials' which are combined to impart a pleasurable scent, odor, or fragrance characteristic”.
  • the term “binary accord” as used herein is defined as "a mixture of two complimentary fragrance raw materials which together deliver a fragrance note”.
  • fragment 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”.
  • fragrance raw materials which comprise the pro-accords of the present invention are not deliverable as individual compounds to fabric via the laundry cycle either due to solubility factors (lost or rinsed away during the laundry cycles), substantivity factors (do not sufficiently adhere to fabric surface), or volatility factors (evaporation during the drying cycle). Therefore, the pro-accords described herein are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered.
  • the preferred pro-accords of the present invention are orthoesters and orthocarbonates.
  • the "fragrance raw materials” which comprise the preferred embodiments are fragrance raw material alcohols.
  • a listing of common fragrance raw material alcohols can be found in various reference sources, for example, “Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and “Perftimes: Art, Science and Technology”; M ⁇ ller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) all of which are incorporated herein by reference.
  • the fragrance accords released by the pro-accords of the present invention have a "heart", "character”, or “note” which is described as inter alia rose, jasmin, lilac, lily of the valley, violet, orange, peach, watermelon, and lemon.
  • the accord may be further "modified” or “twisted” by the use of modifier top or middle notes which, as an additional benefit afforded by the present invention, can be incorporated into the pro-accord.
  • a "rose essence” may be combined with a "green” modifier to "shift the fragrance accord character".
  • freshness For the purposes of the present invention the terms “fresh”, “fresh-like”, “fresh smelling”, “clean”, “clean-like” and “clean smelling” are terms used to describe the sensory effect produced by the release of the fragrance raw materials which comprise the pro-accords of the present invention.
  • the presence of perfume components and fragrance raw materials upon a fabric up to two weeks after washing are regarded as imparting the aforementioned sensory effects.
  • the pro-accords of the present invention are comprised of one or more fragrance raw materials. These fragrance raw materials are then converted into a different chemical form which incorporates the fragrance raw materials in a manner which allows the release of the original fragrance raw material as well as other "newly formed” materials. These chemically modified forms of the fragrance raw materials are the “pro-accords” of the present invention.
  • One principle aspect of the present invention is the ability of pro-accords described herein to deliver more than one fragrance raw material when the "pro-accord" has been formed from only one fragrance raw material. All of the pro-accords of the present invention are capable of releasing at least two fragrance raw materials (hereinafter "binary accord") upon deposition onto fabric.
  • the pro-accords of the present invention generally have a molecular weight of at least 300 g/mol, preferably greater than 325 g/mol, more preferably greater than 350 g/mol. It is also a condition of the present invention that the final molecular weight of the pro-accord is at least 2 times, preferably at least 2.25 times, more preferably 2.5 times, most preferably at least 2.75 times the molecular weight of the lowest fragrance material component.
  • fragrance raw materials having a molecular weight of at least 100 g/mol are considered “fragrance raw materials” according to the present invention. Therefore, low molecular weight materials inter alia methanol, ethanol, methyl acetate, ethyl acetate, and methyl formate which are common components of fragrance accords are excluded from the class of compounds defined herein as "fragrance raw materials”.
  • the formulator may wish to deliver these lower molecular weight materials (less than a molecular weight of 100 g/mol) as carriers, astringents, diluents, balancers, or as other suitable adjunct materials and is therefore not precluded from forming a pro- accord material which delivers, in addition to a fragrance raw material accord, a suitable astringent, carrier, diluent, extender, balancer, etc.
  • a pro-accord which does not comprise a low molecular weight adjunct is present in addition to any pro-accord which releases an adjunct material.
  • the pro-accord tris-geranyl orthoformate is considered, for the purposes of the present invention to be formed from three equivalents of geraniol.
  • This pro-accord releases the binary accord geraniol/geranyl formate.
  • This pro-accord has a molecular weight of approximately 472 g/mol.
  • the lowest molecular weight fragrance raw material which is a component of tris-geranyl orthoformate is geraniol which has a molecular weight of approximately 154 g/mol. Therefore tris-geranyl orthoformate has a molecular weight greater than 3 times the molecular weight of the lowest molecular weight fragrance raw material component (geraniol) and hence is a most preferred pro- accord.
  • substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula: R6
  • substituted or unsubstituted alkyleneoxyalkyl are defined as moieties having the formula:
  • R ⁇ is hydrogen, C ⁇ -C ⁇ $ alkyl, Ci -C4 alkoxy, and mixtures thereof; R ⁇ is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 20 and the index y is from 2 to about 30.
  • substituted or unsubstituted alkylenearyl units are defined as moieties having the formula:
  • R* and R" are each independently hydrogen, hydroxy, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO H; -CO 2 R; -CONH 2 ; -CONHR; - CONR'2; wherein R' is C]-C ⁇ 2 linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is from 1 to about 34.
  • substituted or unsubstituted aryloxy units are defined as moieties having the formula:
  • R- > and R° are each independently hydrogen, hydroxy, C1 -C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO 2 H; -CO 2 R; -CONH 2 ; -CONHR'; - CONR'2; wherein R' is Cj-Ci 2 linear or branched alkyl), amino, alkylamino, and mixtures thereof.
  • substituted or unsubstituted alkyleneoxyaryl units are defined as moieties having the formula: wherein R ⁇ and R" are each independently hydrogen, hydroxy, C ⁇ -C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO2H; -CO2R'; -CONH ; -CONHR'; - CONR'2; wherein R' is C1-C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is from 1 to about 34.
  • substituted or unsubstituted oxyalkylenearyl units are defined as moieties having the formula:
  • R ⁇ and R ⁇ are each independently hydrogen, hydroxy, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO 2 H; -CO2R'; -CONH2; -CONHR'; - CONR'2; wherein R is C ⁇ -C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, w is from 1 to about 34.
  • One class compounds useful as pro-accords according to the present invention are orthoesters having the formula:
  • hydrolysis of the or hoester releases fragrance raw material components according to the following scheme:
  • R is hydrogen, C1 -Cg linear alkyl, C4-C20 branched alkyl, Cg-C20 cyclic alkyl, Cg-C20 branched cyclic alkyl, Cg-C20 linear alkenyl, C6-C20 branched alkenyl, Cg-C20 cyclic alkenyl, Cg-C20 branched cyclic alkenyl, Cg-C20 substituted or unsubstituted aryl, preferably the moieties which substitute the aryl units are alkyl moieties, and mixtures thereof, preferably R is hydrogen, methyl, ethyl, and phenyl.
  • Rl, R2 and R 3 are independently C1-C20 linear, branched, or substituted alkyl; C2-C20 linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; Cg-C20 substituted or unsubstituted aryl, C2-C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxy alkyl; Cg-C40 substituted or unsubstituted alkylenearyl; C6-C32 substituted or unsubstituted aryloxy; Cg-C40 substituted or unsubstituted alkyleneoxy aryl; C6-C40 oxyalkylenearyl; and mixtures thereof.
  • substituted herein is meant "compatible moieties which replace a hydrogen atom".
  • substituents are hydroxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO 2 H; -CO 2 R'; -CONH 2 ; -CONHR'; -CONR' 2 ; wherein R is C1-C12 linear or branched alkyl), amino, C1 -C12 mono- and dialkylamino, and mixtures thereof.
  • Rl, R 2 and R 3 are methyl, 2,4-dimethyl-3-cyclo- hexene-1 -methyl (Floralol), 2,4-dimethyl cyclohexane methyl (Dihydro floralol), 5,6-dimethyl-l -methylethenyl-bicyclo[2.2.1 ]hept-5-ene-2-methyl (Arbozol), 2,4,6- trimethyl-3-cyclohexene-l -methyl (Isocyclo geranyl), 4-(l- methylethyl)cyclohexylmethyl (Mayol), ⁇ -3,3-trimethyl-2-norboranylmethyl, 1,1- dimethyl-l-(4-methylcyclohex-3-enyl)methyl, ethyl, 2-phenylethyl, 2- cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl
  • orthoesters according to the present invention are cyclic orthoesters derived from at least one diol having the formula:
  • R ⁇ , R ⁇ , RIO, and R ⁇ 1 are each independently hydrogen, Ci[-C o linear or branched alkyl, C ⁇ -C 2 o linear or branched alkenyl, C1 -C20 linear, branched or cyclic alkylenecarboxy, C1 -C 2 Q linear, branched, or cyclic carboxyalkyl, C1 -C20 linear or branched alkyleneamino, C1 -C20 linear or branched aminoalkyl, C1 -C20 linear, branched, or cyclic alkylenecarboxamido, C ⁇ -C20 linear or branched carboxamidoalkyl, alkyleneoxy having the formula:
  • Rl3 (OCH 2 CH) x (CH 2 ) yR 12 wherein Rl2 1S hydrogen or methyl; R ⁇ is hydrogen or C ⁇ -C 2 alkyl; n is from 0 to 4, x is from 1 to about 20, y is from 0 to about 20.
  • Rl , R2, or R 3 units may serve to link two pro-accords for the purpose of providing greater substantivity.
  • An example of "pro-accord linking" by a diol has the following formula:
  • Orthoester Releasable Components Hydrolysis of the orthoesters of the present invention result in the delivery of two types of releasable component, namely alcohols and esters. More specifically, hydrolysis of an orthoester yields two equivalents of releasable alcohol, preferably a primary or secondary alcohol and one equivalent of releasable ester. The released ester, when taken together with the released alcohol, forms a binary fragrance accord. For example tris-geranyl orthoformate releases the binary accord geraniol/geranyl formate.
  • esters which are releasable components of the orthoesters of the present invention include, but are not limited to, geranyl formate, citronellyl formate, phenylethyl formate, phenoxyethyl formate, tr ⁇ ws-2-hexenyl formate, cw-3-hexenyl formate, cz ' s- ⁇ -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-dimethylnon
  • Non-limiting examples of alcohols suitably released by the hydrolysis of the orthoester pro-accords include methanol, 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-1 -methanol (Isocyclo geraniol), 4-(l-methylethyl)cyclohexanemethanol (Mayol), ⁇ -3,3-trimethyl-2-norborane methanol, 1,1 -dimethyl- l-(4-methy lcyclohex- 3-enyl)methanol, ethanol, 2-phenylethanol, 2-cyclohexyl ethanol, 2-(o- methylphenyl)-
  • Preferred alcohols released by the orthoesters of the present invention are 4- (l-methylethyl)cyclohexanemethanol (mayol), 2,4-dimethyl-3-cyclohexen-l- ylmethanol (floralol), 2,4-dimethylcyclohex-l-ylmethanol (dihydrofloralol), 2,4,6- trimethyl-3-cyclohexen-l-ylmethanol (isocyclogeraniol), 2-phenylethanol, l-(4- isopropylcyclohexyl)ethanol (mugetanol), 2-(o-methylphenyl)ethanol ⁇ prtho- hawthanol), 2-(m-methylphenyl)ethanol (/wet ⁇ -hawthanol), 2-(p-methylphenyl)- ethanol (p ⁇ r ⁇ -hawthanol), 2,2-dimethyl-3-(3-methylphenyl)propan-l-ol (majantol), 3-phen
  • Non-limiting examples of orthoester pro-accords according to the present invention are tris(geranyl orthoformate, tris(cw-3-hexen-l-yl) orthoformate, tris(phenylethyl) orthoformate, bis(citronellyl) ethyl orthoacetate, tris(citronellyl) orthoformate, tris(cz ' 5 , -6-nonenyl) orthoformate, tris(phenoxyethyl) orthoformate, tris(geranyl, neryl) orthoformate (70:30 geranykneryl), tris(9-decenyl) orthoformate, tris(3-methyl-5-phenylpentanyl) orthoformate, tris(6-methylheptan-2-yl) orthoformate, tris([4-(2,2,6-trimethyl-2-cyclohexen-l-yl)-3-buten-2-yl] orthoformate, tris[3
  • Orthoester pro-accords can be used to deliver inter alia binary fragrance accords, fragrance accords having a "binary characteristic" accord component in combination with a modifier accord, and fragrance accords comprising astringents, fixatives, or diluents.
  • orthocarbonate pro-accords of the present invention have the general formula:
  • Rl, R 2 , R3, and R ⁇ are independently Cj-C20 linear, branched, or substituted alkyl; C2-C 2 Q linear, branched, or substituted alkenyl; C5-C20 substituted or unsubstituted cyclic alkyl; C6-C 2 o substituted or unsubstituted aryl, C2-C40 substituted or unsubstituted alkyleneoxy; C3-C40 substituted or unsubstituted alkyleneoxy alkyl; C -C40 substituted or unsubstituted alkylenearyl; Cg-C40 substituted or unsubstituted aryloxy; C6-C40 substituted or unsubstituted alkyleneoxy aryl; any two R* , R 2 , R J ?
  • R4 are taken together to form a ring having from 5 to 7 atoms wherein said ring is substituted or unsubstituted; and mixtures thereof; preferably at least two of the moieties Rl, R2, R3, and R4 are derived from a fragrance raw material alcohol, more preferably at least three of the moieties Rl, R R3. and R ⁇ are derived from a fragrance raw material alcohol, most preferably each Rl, R 2 , R3. and R ⁇ is derived from a fragrance raw material alcohol.
  • Rl, R 2 , R3, and R ⁇ are methyl, 2,4-dimethyl-3- cyclo-hexene-1 -methyl (Floralol), 2,4-dimethyl cyclohexane methyl (Dihydro floralol), 5,6-dimethyl-l-methylethenyl-bicyclo[2.2.1]hept-5-ene-2-methyl (Arbozol), 2,4,6-trimethyl-3-cyclohexene-l -methyl (Isocyclo geranyl), 4-(l- methylethyl)cyclohexylmethyl (Mayol), ⁇ -3,3-trimethyl-2-norboranylmethyl, 1,1- dimethyl-l-(4-methylcyclohex-3-enyl)methyl, ethyl, 2-phenylethyl, 2- cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)eth
  • the carbonate which is released by the orthocarbonate may be a fragrance raw material precursor or itself a pro-accord (capable of releasing two different fragrance raw materials), preferably the carbonate which is released serves as a fragrance raw material, fixative, etc.
  • An orthocarbonate which comprises four different fragrance raw materials will always release a carbonate that is a pro-accord (hydrolyzes to release a binary accord) in addition to any further fragrance properties attributable to the carbonate.
  • the alcohols which are released by the orthocarbonate pro-accords of the present invention may be "fragrance raw material alcohols", astringent alcohols, disinfectant alcohols, or carrier alcohols.
  • fragment raw material alcohols are defined herein as "alcohols having a molecular weight greater than 100 g/mol and which when used alone or in combination with other fragrance raw material alcohols have a generally pleasurable odor”.
  • Non limiting examples of alcohols which can be suitably released by the orthocarbonate pro-accords of the present invention are methanol, 2,4-dimethyl-3- cyclohexene-1 -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-1 -methanol (Isocyclo geraniol), 4-(l- methylethyl)cyclohexanemethanol (Mayol), ⁇ -3,3-trimethyl-2-norborane methanol, 1,1 -dimethyl- l-(4-methylcyclohex-3-enyl)methanol, ethanol, 2-phenylethanol, 2- cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol
  • Preferred alcohols released by the orthocarbonate pro-accords of the present invention are 4-(l-methylethyl)cyclohexanemethanol (mayol), 2,4-dimethyl-3- cyclohexen- 1 -ylmethanol (floralol), 2,4-dimethy lcyclohex- 1 -ylmethanol (dihydrofloralol), 2,4,6-trimethyl-3-cyclohexen-l -ylmethanol (isocyclogeraniol), 2- phenylethanol, l-(4-isopropylcyclohexyl)ethanol (mugetanol), 2-(o-mefhylphenyl)- ethanol (ort zo-hawthanol), 2-(m-methylphenyl)ethanol (met ⁇ -hawfhanol), 2-(p- methylphenyl)ethanol (p ⁇ r -hawthanol), 2,2-dimethyl-3-(3-methylphenyl)
  • the orthocarbonates according to the present invention can be formed from at least one diol having the formula:
  • R ⁇ , R9, R10 ? anf j R11 a re each independently hydrogen, Ci -C 2 Q linear or branched alkyl, Cj-C 2 o linear or branched alkenyl, Cj-C 2 o linear, branched or cyclic alkylenecarboxy, C ⁇ -C 2 ⁇ linear, branched, or cyclic carboxyalkyl, Ci -C Q linear or branched alkyleneamino, CI -C 2 Q linear or branched aminoalkyl, Ci -C 2 o linear, branched, or cyclic alkylenecarboxamido, Ci -C20 linear or branched carboxamidoalkyl, alkyleneoxy having the formula:
  • Rl3 (OCH 2 CH) x (CH 2 ) yR 12 wherein R 2 is hydrogen or methyl; Rl is hydrogen or Ci -C 2 alkyl; n is from 0 to 4, x is from 1 to about 20, y is from 0 to about 20.
  • An example of a cyclic orthocarbonate having one R& or R ⁇ unit which is a Ci -C20 linear, branched, or cyclic alkyl has the formula:
  • R 2 and R are each cw-3-hexenyl.
  • cyclic orthocarbonate having one R ⁇ or R ⁇ unit which is a Ci -C20 linear, branched, or cyclic alkylenecarboxy has the formula:
  • R 2 and R are each citronellyl.
  • cyclic orthocarbonate having one R or R ⁇ unit which is a Ci -C20 linear, branched, or cyclic alkylenecarboxy has the formula:
  • R 2 and R3 are each 2-phenylethyl.
  • cyclic orthocarbonate having one R° or R" unit which is a C1-C20 linear, branched, or cyclic alkyleneamido has the formula: wherein R 2 and R3 are each vanillyl bis(methoxy) acetal.
  • cyclic orthocarbonate having one R ⁇ > or R ⁇ unit which is a C1-C20 linear, branched, or cyclic alkyleneamino has the formula:
  • R 2 and R are each c «-3-hexenyl.
  • a further preferred orthocarbonate has the R& or R unit taken together to form a spiro bis(orthocarbonate) an example of which has the formula:
  • R 2 and R units of each orthoester is a 2-phenylethyl moiety.
  • an R , R2, R3. or R unit may serve to link two pro-accords for the purpose of providing greater substantivity.
  • An example of pro-accords linking by a diol has the following formula:
  • the more preferred orthocarbonate pro-accords of the present invention comprise at least three of the R , R 2 , R ; and R4 moieties which are derived from a fragrance raw material alcohol, thereby the preferred pro-fragrances have a molecular weight which is at least 3 times the molecular weight of the lowest "fragrance raw material alcohol" which comprises the orthocarbonate pro-fragrance. Further, the more preferred orthocarbonate pro-fragrances have a molecular weight which is greater than or equal to 325 g/mol.
  • Non-limiting examples of more preferred orthocarbonate pro-accords according to the present invention include: methyl tris(geranyl) orthocarbonate, ethyl tris(geranyl) orthocarbonate, methyl tris(phenylethyl) orthocarbonate, ethyl tris(phenylethyl) orthocarbonate, methyl tris(cis-3 -hexenyl) orthocarbonate, ethyl tris(cz5-3-hexenyl) orthocarbonate, methyl tris(citronellyl) orthocarbonate, ethyl tris(citronellyl) orthocarbonate, methyl tris(linalyl) orthocarbonate, ethyl tris(linalyl) orthocarbonate, methyl tris(menthyl) orthocarbonate, ethyl tris(menthyl) orthocarbonate, dodecyl tris(geranyl) orthocarbonate, and dodecyl tris(phenylethyl
  • the most preferred orthocarbonate pro-accords of the present invention have each of the R ⁇ , R 2 , R3, and R4 moieties derived from a fragrance raw material alcohol, thereby the preferred pro-fragrances have a molecular weight which is at least 4 times the molecular weight of the lowest "fragrance raw material alcohol" which comprises the orthocarbonate pro-accord. Further, the preferred orthocarbonate pro-accords have a molecular weight which is greater than or equal to 350 g/mol.
  • Non-limiting examples of most preferred orthocarbonate pro-accords according to the present invention include: tetra-geranyl orthocarbonate, tetra- phenylethyl orthocarbonate, tetrakis(3-methyl-5-phenylpentyl) orthocarbonate, tetrakis(cz5 , -3 -hexenyl) orthocarbonate, bis(geranyl) bis(cz ' 5-3 -hexenyl) orthocarbonate, bis(phenylethyl) bis(czs-3 -hexenyl) orthocarbonate, tetrakis(citronellyl) orthocarbonate, tetrakis(linalyl) orthocarbonate, bis(linallyl) bis(geranyl) orthocarbonate, tetrakis(myrcenyl) orthocarbonate, tetrakis(cinnamyl) orthocarbonate.
  • the pro-accords useful in the laundry detergent compositions of the present invention generally have high substantivity. This high substantivity is a prerequisite in that the pro-accord must be suitably deposited upon the target fabric in order for the pro-accords of the present invention to be in a position to provide the increased fragrance longevity benefits described herein.
  • the pro-accords of the present invention can be formulated to deliver the fragrance accords over any time period useful to the formulator, for example, within a time period desirable to the consumer.
  • the pro-accords generally have a "Fragrance Release Half-life" of less than or equal to about 1 hour when measured in 1 N HCl buffer at pH 0, more preferably a "fragrance release half-life” of less than or equal to about 12 hours when measured in NaH2PO4 buffer at pH 2.5.
  • the "Fragrance Release Half-life” is defined herein as follows.
  • Pro-accords deliver their corresponding mixture of fragrance raw materials or fragrance accords according to the equation:
  • Pro-Accord ⁇ Accord wherein the accord which is released may be a binary accord or a multiple fragrance raw material accord.
  • Rate k[Pro-accord] and can be further expressed by the formula:
  • the HCl buffered water is obtained by using a 1 N HCl volumetric standard solution (available from J. T. Baker).
  • the phosphate buffered water is prepared by admixing 5.6 gm of phosphoric acid (H3PO4) and 26.3 gm of sodium dihydrogen phosphate (NaH2PO4) with one liter of de-ionized water. The pH values of the aqueous solutions are confirmed using a pH meter.
  • aqueous buffer 10 mL is admixed with 90 mL of dioxane (99.9% HPLC grade, available from Sigma Aldrich) and is preheated to 30° C.
  • dioxane 99.9% HPLC grade, available from Sigma Aldrich
  • the preheated 90/10 dioxane/acid buffered water is then added to the pro-accord and the hydrolysis kinetics are then monitored by conventional HPLC techniques at 30° C.
  • the amount of pro-accord used is less than one-tenth the amount of water on a molar basis to insure pseudo first-order kinetic conditions.
  • Pro-accords having t ⁇ /2 less than 1 hour in pH 0 HCl buffer show fragrance release benefits on surfaces such as fabric articles over weeks, and exhibit a delayed onset to these benefits after laundering. More preferably, the pro-accords have a tj/ 2 less than 12 hours in pH 2.5 phosphate buffer which show fragrance release benefits which are noticeable immediately after conclusion of the wash and which extend for several days up to two weeks.
  • Table I lists several pro-accords according to the present invention with their corresponding t 1 2 (at pH 2.5) values.
  • tris(phenylefhyl) orthoformate is suitable for use as a pro-fragrance for delivering a "rose-floral" character note to an accord having enhance longevity.
  • the hydrolysis rate, and therefore the determination of t 1 2 must be measured in a buffer system which can accommodate this more rapid hydrolysis rate.
  • the pro-fragrance tris(phenylethyl) orthoacetate is used to deliver a rapid onset of a "rose-floral" middle note by releasing the fragrance raw material phenylethyl alcohol.
  • the relative release rate of this pro-accord can be suitably determined by substituting a phosphate buffer comprising 4.6 gm of sodium dihydrogen phosphate (NaH2PO4) and 7.9 gm of disodium hydrogen phosphate (Na2HPO4) admixed with 1 liter of water for the phosphate buffer described herein above.
  • a phosphate buffer comprising 4.6 gm of sodium dihydrogen phosphate (NaH2PO4) and 7.9 gm of disodium hydrogen phosphate (Na2HPO4) admixed with 1 liter of water for the phosphate buffer described herein above.
  • the pro-accords of the present invention are stable under pH conditions encountered in the formulation and storage of detergent products which have a pH of from about 7.1 to 13, and during solution-use of such products. Due to their high molecular weight and hydrophobicity, these pro-accord compounds give reasonably good deposition from a laundering solution onto fabrics. Because the pro-accords are subject to hydrolysis when the pH is reduced, they hydrolyze to release their component fragrance compounds when the fabrics upon which they have been deposited are exposed even to reduced pH such as present in rinse water, air and humidity.
  • the reduction in pH should be at least 0.1, preferably at least about 0.5 units.
  • the pH is reduced by at least 0.5 units to a pH of 7.5 or less, more preferably 6.9 or less.
  • the solution in which the fabric (or other surface) is washed is alkaline.
  • the pro-accords of the present invention in addition have a ClogP value of at least greater than or equal to 3, preferably greater than or equal to 4, more preferably greater than or equal to 5, most preferably greater than or equal to 6.
  • the pro-accords of the invention are characterized by their octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a pro-accord is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of the pro-accord compounds are large, they are more conveniently given in the form of their logarithm to the base 10, logP.
  • CLogP The "calculated logP” (CLogP) is determined by the fragment approach of Hansch and Leo (eft, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and CA. Ramsden, Eds., p. 295, Pergamon Press, 1990).
  • the fragment approach is based on the chemical structure of a compound and takes into account the numbers and type of atoms, the atom connectivity, and chemical bonding.
  • the CLogP values which are the most reliable and widely used estimates for this physicochemical property, can be used instead of the experimental logP values in the selection of pro-accords.
  • Symmetrical pro-accords are pro-accords which release the same fragrance raw materials regardless of hydrolysis pathway.
  • An example of a symmetrical pro- accord is tris(phenylethyl) orthoacetate which releases a binary accord having a "rose" characteristic comprising 2 parts phenylethyl alcohol and 1 part phenylethyl acetate according to the following scheme:
  • phenylethyl alcohol/phenylethyl acetate (2:1) binary accord depicted above is useful in delivering to fabric a rose or rose/floral characteristic.
  • phenylethyl alcohol and phenylethyl acetate are the only fragrance raw materials which are releasable by this binary pro-accord regardless of hydrolysis pathway.
  • Unsymmetrical pro-accords have the capacity to release fragrance accords more complex than the binary fragrance accords released by symmetrical pro- accords.
  • the composition of the released accord depends on the route of pro-accord hydrolysis.
  • An unsymmetrical pro-accord can be designed by the formulator to release different ratios of fragrance raw materials based not only on the composition of the pro-accord but on the reactivity as well.
  • unsymmetrical pro- accords can also be used to produce "adjunct pro-accords" useful for releasing low molecular weight modifiers, fixatives, carriers, astringents, etc., in addition to fragrance raw materials.
  • An example of an unsymmetrical pro-accord is bis(citronellyl) benzyl orthoacetate capable of releasing the binary fragrance accord of citronellol/citronellyl acetate having a "rose” characteristic together with the benzyl alcohol/benzyl acetate "jasmin" modifiers according to the following scheme:
  • the above accord can be suitably modified by the formulator to adjust the relative proportions of the accord ingredients.
  • more of the "sweet" character diluent benzyl alcohol can be delivered by adjusting the proportion of citronellol and benzyl alcohol used to formulate the pro-accord.
  • Bis(benzyl) citronellyl orthoacetate delivers the same fragrance raw materials as bis(citronellyl) benzyl orthoacetate, only the relative amounts of the released materials differ.
  • the present invention also relates to a method for providing a sustained fragrance to fabric comprising the step of contacting fabric with an aqueous solution of a laundry detergent composition comprising: a) at least about 0.01%, preferably from about 0.01% to about 10%, more preferably from about 0.1% to about 1% by weight, of a fragrance delivery system comprising one or more pro-accords said pro-accords formed from at least one fragrance raw material and capable of releasing two or more fragrance raw materials wherein provided each pro-accord: i) comprises fragrance raw materials having a molecular weight greater than or equal to 100 g/mol; ii) has a molecular weight greater than or equal to 300 g/mol; iii) has a molecular weight at least two times greater than the lowest molecular weight fragrance raw material which comprises said pro-accord; and iv) has a fragrance release half-life of less than about 1 hour when measured in a 90:10 dioxane/1 N HCl mixture at pH 0, preferably a fragrance release half-
  • the instant cleaning compositions may contain at least about 0.01 % by weight of a surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surface active agents.
  • a surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surface active agents.
  • surfactant is preferably present to the extent of from about 0.1 % to 60 %, more preferably 0.1% to about 30% by weight of the composition.
  • Nonlimiting examples of surfactants useful herein typically at levels from about P/o to about 55%, by weight include the conventional Ci j-C ⁇ g alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C ⁇ 0-C20 alkyl sulfates (“AS”), the CiQ-Ci secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO3 " M + ) CH 3 and CH 3 (CH2)y(CHOSO 3 " M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the CJO-CI g alkyl alkoxy sulfates ("AE X S”; especially EO 1-7 ethoxy sulfates), CjQ-Cig alkyl alkoxy carb
  • the conventional nonionic and amphoteric surfactants such as the Cj 2 -C ⁇ g alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-Cj 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ⁇ 2 -Cjg betaines and sulfobetaines ("sultaines”), C ⁇ Q-Ci amine oxides, and the like, can also be included in the overall compositions.
  • AE alkyl ethoxylates
  • C6-Cj 2 alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
  • C ⁇ 2 -Cjg betaines and sulfobetaines sultaines
  • C ⁇ Q-Ci amine oxides and the like
  • the CjQ-Ci N-alkyl polyhydroxy fatty acid amides are highly
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cio-Cj N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C ⁇ -Cig glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain ⁇ Q-C ⁇ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
  • Other conventional useful surfactants are described further herein and are listed in standard texts.
  • Anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • alkyl is the alkyl portion of higher acyl radicals.
  • anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of a higher fatty alcohol (e.g.
  • tallow or coconut alcohols and about 1 to about 10 moles of ethylene oxide
  • the reaction products of fatty acids are derived from coconut oil sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
  • secondary alkyl sulfates may be used by the formulator exclusively or in conjunction with other surfactant materials and the following identifies and illustrates the differences between sulfated surfactants and otherwise conventional alkyl sulfate surfactants.
  • Non-limiting examples of such ingredients are as follows.
  • Conventional primary alkyl sulfates such as those illustrated above, have the general formula ROSO3-M+ wherein R is typically a linear C8-22 hydrocarbyl group and M is a water solublizing cation.
  • Branched chain primary alkyl sulfate surfactants i.e., branched-chain "PAS" having 8-20 carbon atoms are also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed January 21, 1991.
  • Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH 3 (CH2) n (CHOSO 3 -M+)(CH2) m CH3 wherein m and n are integers of 2 of greater and the sum of m + n is typically about 9 to 17, and M is a water-solublizing cation.
  • the aforementioned secondary alkyl sulfates are those prepared by the addition of H2SO4 to olefins.
  • a typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued February 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. See also U.S. Patent 5,349,101, Lutz et al., issued September 20, 1994; U.S. Patent 5,389,277, Prieto, issued February 14, 1995.
  • the preferred surfactants of the present invention are anionic surfactants, however, other surfactants useful herein are described below.
  • compositions of the present invention can also comprise at least about 0.01%, preferably at least 0.1%, more preferably from about 1% to about 30%, of an nonionic detersive surfactant.
  • Preferred nonionic surfactants such as C ⁇ 2 -C ⁇ alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C - C] 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of C5 to Ci 2 alkyl phenols, alkylene oxide condensates of Cg-C 22 alkanols and ethylene oxide/propylene oxide block polymers (PluronicTM-BASF Corp.), as well as semi polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions.
  • AE C ⁇ 2 -C ⁇ alkyl ethoxylates
  • Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado (incorporated herein by reference) are also preferred nonionic surfactants in the compositions of the invention.
  • More preferred nonionic surfactants are the polyhydroxy fatty acid amides having the formula:
  • Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof.
  • Preferred Q is derived from a reducing sugar in a reductive amination reaction. More preferably Q is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above.
  • Q is more preferably selected from the group consisting of -CH 2 (CHOH) n CH 2 OH, -CH(CH 2 OH)(CHOH) n . 1 CH OH, -CH (CHOH) 2 -(CHOR')(CHOH)CH 2 OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R is hydrogen or a cyclic or aliphatic monosaccharide. Most preferred substituents for the Q moiety are glycityls wherein n is 4, particularly -CH 2 (CHOH)4CH 2 OH.
  • R ' * C0-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • R° can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or 2-hydroxy propyl.
  • Q can be 1 -deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1 -deoxygalactityl, 1 -deoxymannityl, 1-deoxymaltotriotityl, etc.
  • a particularly desirable surfactant of this type for use in the compositions herein is alkyl-N-mefhyl glucomide, a compound of the above formula wherein R ⁇ is alkyl (preferably C ⁇ ⁇ -C ⁇ ), R°, is methyl and Q is 1 -deoxyglucityl.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Ci Q-Cj N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C ⁇ -Cj glucamides can be used for low sudsing.
  • Ci o-C 2 0 conventional soaps may also be used. If high sudsing is desired, the branched-chain CJ Q-CI O soaps may be used.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1 % builder. Formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%), more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function su ⁇ risingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 mo ⁇ hology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O 2x + ⁇ -yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amo ⁇ hous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the pu ⁇ oses of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-Q20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • compositions of the present invention can also optionally contain water- soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • CMC carboxy methyl cellulose
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar compositions, etc.
  • Other optional ingredients include enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners, hydrolyzable surfactants, optical brighteners, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, soil release agents, germicides, fungicides, and anti corrosion agents.
  • suds boosters such as the Ci 0-C1 alkanolamides can be inco ⁇ orated into the compositions, typically at 1%-10% levels.
  • the Ci -C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl 2 , MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of Ci 3.15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosity in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosity in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergent compositions.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the pro-accords of the present invention can be used in both low density (below 550 grams/liter) and high density granular compositions in which the density of the granule is at least 550 grams/liter.
  • Granular compositions are typically designed to provide an in the wash pH of from about 7.5 to about 11.5, more preferably from about 9.5 to about 10.5.
  • Low density compositions can be prepared by standard spray-drying processes.
  • Various means and equipment are available to prepare high density compositions. Current commercial practice in the field employs spray-drying towers to manufacture compositions which have a density less than about 500 g/1. Accordingly, if spray-drying is used as part of the overall process, the resulting spray-dried particles must be further densified using the means and equipment described hereinafter.
  • the formulator can eliminate spray-drying by using mixing, densifying and granulating equipment that is commercially available. The following is a nonlimiting description of such equipment suitable for use herein.
  • high density i.e., greater than about 550, preferably greater than about 650, grams/liter or "g/1"
  • high solubility, free-flowing, granular detergent compositions according to the present invention.
  • Current commercial practice in the field employs spray-drying towers to manufacture granular laundry detergents which often have a density less than about 500 g/1.
  • an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175°C to about 225°C.
  • additional process steps as described hereinafter must be used to obtain the level of density (i.e., > 650 g/1) required by modern compact, low dosage detergent products.
  • spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers.
  • a suitable high speed mixer/densifier for this process is a device marketed under the tradename "L ⁇ dige CB 30" or “Lodige CB 30 Recycler” which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon.
  • the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 ⁇ m to provide thorough mixing/densification.
  • the preferred residence time in the high speed mixer/densifier is from about 1 to 60 seconds.
  • Other such apparatus includes the devices marketed under the tradename “Shugi Granulator” and under the tradename “Drais K-TTP 80).
  • Another process step which can be used to density further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower intraparticle porosity.
  • Equipment such as that marketed under the tradename "L ⁇ dige KM" (Series 300 or 600) or “Lodige Ploughshare” mixer/densifiers are suitable for this process step.
  • Such equipment is typically operated at 40-160 ⁇ m.
  • the residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes.
  • Other useful equipment includes the device which is available under the tradename "Drais K-T 160".
  • This process step which employs a moderate speed mixer/densifier e.g. Lodige KM
  • can be used by itself or sequentially with the aforementioned high speed mixer/densifier e.g. Lodige CB
  • Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942.
  • the reverse sequential mixer/densifier configuration is also contemplated by the invention.
  • One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention.
  • adjunct ingredients such as liquid binders and flow aids
  • Patent 4,637,891 issued January 20, 1987 (granulating spray- dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate).
  • the formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing/densifying equipment that is commercially available.
  • One particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material into a high speed mixer/densifier (e.g. Lodige CB) followed by a moderate speed mixer/densifier (e.g. Lodige KM) to form high density detergent agglomerates.
  • a high speed mixer/densifier e.g. Lodige CB
  • a moderate speed mixer/densifier e.g. Lodige KM
  • liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp.
  • the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up.
  • the oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment.
  • These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550 g/1). See Capeci et al, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996.
  • the high density detergent composition of the invention can be produced using a fluidized bed mixer.
  • the various ingredients of the finished composition are combined in an aqueous slurry (typically 80%) solids content) and sprayed into a fluidized bed to provide the finished detergent granules.
  • this process can optionally include the step of mixing the slurry using the aforementioned Lodige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes.
  • Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients.
  • a high speed mixer/densifier e.g. Lodige KM
  • a moderate speed mixer/densifier e.g. Lodige KM
  • reaction progress is monitored by the amount of ethanol generated and by silica gel thin layer chromatography (TLC) eluting with 4% ethyl acetate/petroleum ether and development with iodine stain.
  • TLC silica gel thin layer chromatography
  • the reaction mixture is diluted with diethyl ether (200 mL) and the organic phase washed three times with saturated aqueous sodium carbonate.
  • the organic phase was dried over magnesium sulfate, filtered, and the resulting clear solution is concentrated in vacuo.
  • the product is purified by Kugelrohr distillation wherein the fraction in the range 140-150° C, at 0.1 mm Hg is collected to yield 23.5 g (73%).
  • phenylethyl alcohol 100 g
  • trimethylorfhoacetate 30 g
  • 3 drops of concentrated sulfuric acid Nitrogen is slowly bubbled through the solution over a 4 day period to remove the methanol which is produced.
  • the mixture is then diluted in diethyl ether (300 mL) and washed three times with saturated aqueous sodium carbonate.
  • the organic phase is dried over magnesium sulfate, filtered, and the resulting clear solution is concentrated.
  • phenylethyl alcohol 36.7 g
  • tretraethylorthocarbonate 9.84 g
  • para- toluenesulfonic acid monohydrate 0.21 g
  • Nitrogen is slowly bubbled through the solution while stirring over 36 hr to remove the ethanol which is produced.
  • the mixture is then diluted with diethyl ether (300 mL) and washed three times with saturated aqueous sodium carbonate. The organic phase is dried over magnesium sulfate, filtered, and concentrated.
  • EXAMPLES 8 - 16 The following are examples of granular detergent compositions comprising fragrance pro-accords.
  • Soil release polymer according to U.S. Patent 4,968,451 , Scheibel et al., issued November 6, 1990.
  • Soil release polymer according to U.S. Patent 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
  • Pro-accord comprising tris(geranyl) orthoacetate.
  • Pro-accord mixture comprising 80% tris(phenylethyl) orthoacetate and 20%> tris(cis-3 -hexenyl) orthoformate.
  • Balance to 100% can, for example, include minors like optical brightener, perfume, suds suppresser, soil dispersant, protease, lipase, cellulase, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc, silicates, etc.
  • liquid laundry detergent compositions comprising fragrance pro-accords.
  • Pro-accord comprising tris(phenylethyl) orthoacetate.
  • EXAMPLE 17 The following is an example of a solid bleaching compositon which comprises a pro-accord according to the present invention.
  • EXAMPLE 18 The following is an example of a liquid bleaching composition comprising a pro-accord of the present invention.

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Abstract

La présente invention concerne un système de diffusion de parfum destiné à être utilisé dans des compositions de détergents à lessive, et qui donne au tissu une odeur de 'fraîcheur' ou de 'propreté' durable. Les compositions selon l'invention diffusent sur la surface du tissu, au cours du lavage, des composés diffuseurs de parfum très efficaces sur tissu. Lesdits composés diffuseurs de parfum diffusent leurs parfums sur une période pouvant aller jusqu'à deux semaines. La présente invention concerne également un procédé de diffusion, sur un tissu, d'une odeur agréable procurant une fraîcheur durable, lequel procédé consiste à mettre le tissu au contact d'une composition de détergents à lessive renfermant lesdits composés diffuseurs de parfum.
PCT/US1998/007935 1997-04-24 1998-04-23 Compositions de detergents a lessive renfermant des composes diffuseurs de parfum WO1998047996A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000072816A1 (fr) * 1999-06-01 2000-12-07 The Procter & Gamble Company Proparfums
US6861402B1 (en) 1999-06-01 2005-03-01 The Procter & Gamble Company Pro-fragrances
DE102005042054A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Parfümhaltige Teilchen mit verbesserten Dufteigenschaften
WO2017066400A1 (fr) 2015-10-13 2017-04-20 The Sun Products Corporation Système à plusieurs étages d'administration d'un agent bénéfique
WO2020260598A1 (fr) * 2019-06-27 2020-12-30 Firmenich Sa Produits de consommation parfumés

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5378468A (en) * 1992-09-22 1995-01-03 The Mennen Company Composition containing body activated fragrance for contacting the skin and method of use
EP0771785A1 (fr) * 1995-11-02 1997-05-07 The Procter & Gamble Company Béta-aminoesters d'alcools parfumants et leur utilisation dans des compositions nettoyantes et des compositions détergentes
WO1997034986A1 (fr) * 1996-03-22 1997-09-25 The Procter & Gamble Company Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5378468A (en) * 1992-09-22 1995-01-03 The Mennen Company Composition containing body activated fragrance for contacting the skin and method of use
EP0771785A1 (fr) * 1995-11-02 1997-05-07 The Procter & Gamble Company Béta-aminoesters d'alcools parfumants et leur utilisation dans des compositions nettoyantes et des compositions détergentes
WO1997034986A1 (fr) * 1996-03-22 1997-09-25 The Procter & Gamble Company Compositions detergentes contenant des precurseurs de fragrance et precurseurs de fragrance

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000072816A1 (fr) * 1999-06-01 2000-12-07 The Procter & Gamble Company Proparfums
US6861402B1 (en) 1999-06-01 2005-03-01 The Procter & Gamble Company Pro-fragrances
DE102005042054A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Parfümhaltige Teilchen mit verbesserten Dufteigenschaften
WO2017066400A1 (fr) 2015-10-13 2017-04-20 The Sun Products Corporation Système à plusieurs étages d'administration d'un agent bénéfique
WO2020260598A1 (fr) * 2019-06-27 2020-12-30 Firmenich Sa Produits de consommation parfumés

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