WO1999000377A1 - Pro-fragrance cyclic acetals - Google Patents
Pro-fragrance cyclic acetals Download PDFInfo
- Publication number
- WO1999000377A1 WO1999000377A1 PCT/US1998/013278 US9813278W WO9900377A1 WO 1999000377 A1 WO1999000377 A1 WO 1999000377A1 US 9813278 W US9813278 W US 9813278W WO 9900377 A1 WO9900377 A1 WO 9900377A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- mixtures
- substituted
- fragrance
- unsubstituted
- Prior art date
Links
- 0 CC1(*)C(*)(*)C(O*)OC1(C)* Chemical compound CC1(*)C(*)(*)C(O*)OC1(C)* 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/507—Compounds releasing perfumes by thermal or chemical activation
-
- 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
Definitions
- the present invention relates to pro-fragrance compounds useful in laundry detergent compositions.
- the pro-fragrance compounds comprise a fragrance raw material component and a solubility or substantivity component which can be independently adjusted to meet the specific requirements of the formulator.
- the pro- fragrance compounds are especially useful for delivering a "through the wash” freshlike or clean-like fragrance to fabric which remains on the fabric and is continuously released for extended periods after the conclusion of the laundry cycle.
- 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.
- fragrance delivery system wherein perfume raw materials are delivered to fabric by way of a laundry detergent, rinse-added composition, or dryer-added article of manufacture which provides the cleaned clothing or fabric with a "fresh” or “clean” smell for a period up to two weeks after washing.
- fragrance releasing compounds which deliver a "fresh” or “clean” fragrance in which the solubility and substantivity properties of the compound can be varied to match various formulation and delivery parameters inter alia compatibility with surface active adjuncts and fabric type.
- a fragrance delivery system suitable for providing sustained release or enhanced longevity fragrances to a variety of personal care and personal hygiene products wter alia deodorants, body lotions or creams, and shampoos.
- the present invention meets the aforementioned needs in that it has been surprisingly discovered that certain cyclic acetals can be used to deliver perfume or fragrance raw materials onto fabric "through the wash” from a single precursor pro- fragrance molecule having variable fabric substantivity, variable solubility as well as variable fragrance release rate.
- These pro-fragrances can be used to deliver tertiary alcohol raw materials as well as primary and secondary fragrance raw material alcohols which impart a "fresh" or "clean” aesthetic odor benefit to fabric or to human skin when the skin is contacted with a personal care or personal hygiene product inter alia deodorants, body lotions or creams, and shampoos, which comprises the pro-fragrances of the present invention.
- the pro-fragrances 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-fragrance.
- the pro-fragrances described herein comprise fragrance raw materials in a stable, releasable form.
- the pro-fragrance containing laundry detergent compositions of the present invention can comprise any number of pro-fragrances and are suitable for delivery of any type of fragrance "characteristic" desired by the formulator.
- the first aspect of the present invention relates to pro-fragrance compounds having the formula:
- R is a fragrance raw material alcohol, preferably linalool or dihydromyrcenol
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from: a) hydrogen; b) C j -C22 linear or branched alkyl; c) 2-C22 linear or branched alkenyl; d) C j -C22 linear or branched alkoxy ; e) C6-C20 substituted or unsubstituted aryl; f) 2-C20 substituted or unsubstituted alkyleneoxy; g) 3-C20 substituted or unsubstituted alkyleneoxyalkyl; h) Cg-C20 substituted or unsubstituted alkylenearyl; i) 6-C20 substituted or unsubstituted aryloxy; j) C7-C20 substituted or unsubstituted alkyleneoxyary
- R 9 is -CHO, -CO M; -CO 2 R 10 , -CONH 2 , -CONHR 10 , -CONR ⁇ R ⁇ l, and mixtures thereof; wherein R ⁇ O and R ⁇ 1 are each independently C1 -C ⁇ 2 linear or branched alkyl, M is hydrogen or a salt forming cation, x is an integer from 0 to 19; m) any two R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 units can be taken together to form a fused aromatic or non-aromatic ring comprising from 4 to 7 carbon atoms; n) two or more R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 units can be taken together to form a bicyclic, tricyclic, or spiroannulated ring comprising from 5 to 8 carbon atom
- R 12 is -SO3M, -OSO3M, -PO3M, -OPO3M, or mixtures thereof; wherein M is hydrogen, one or more salt forming cations sufficient to satisfy charge balance, or mixtures thereof; y is an interger from 1 to about 22; p) and mixtures thereof.
- the present invention also relates to laundry detergent compositions which comprise the pro-fragrance cyclic acetals described herein.
- a further aspect of the present invention is the use of the cyclic pro-fragrances of the present invention as a post-laundry "freshening agent" for use on fabric which has been laundered but which has not been worn for an extended period of time.
- a yet further aspect of the present invention is the use of the pro-fragrances of the present invention in rinse- added compositions and in dryer-added compositions.
- the pro-fragrance compounds of the present invention are also capable of delivering sustained release or enhanced longevity fragrances to a variety of personal care and personal hygiene products inter alia deodorants, body lotions or creams, and shampoos.
- the pro-fragrances of the present invention comprise a fragrance raw material component and a substantivity or solubility component.
- the fragrance raw material component can be any perfume or any "fragrance raw material alcohol" which the formulator wishes to deliver to the fabric surface for subsequent release after the laundry cycle.
- the pro-fragrances comprise a substantivity or solubility component wherein the proper choice of group allows the formulator to control the solubility of the pro-fragrance in water, the degree of substantivity of the pro-fragrance for fabric, or the bulk properties of the material.
- pro-fragrance bulk properties will allow the formulator to produce a pro- fragrance which is more easily admixed into a particular type of laundry composition, for example, liquid, granular, high density, encapsulated-component, rinse-added, dryer-added, etc.
- pro-fragrances according to the present invention can also be designed to be activated by a change in pH or to be moisture or “heat activated” so as to release a "freshening scent” to the fabric during drying. Therefore, heat-activated pro-fragrances 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 pro-fragrances.
- heat activated pro-fragrances 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-fragrances of the present invention are therefore a means for delivering a desired fragrance raw material onto fabric and thereby providing the fabric with a longer and more sustained "fresh" or “clean” smell.
- fragrance raw material alcohol is defined as "an alcohol generally having a molecular weight greater than or equal to 100 g/mol which provides a fragrance, scent, smell, odor, or character which is generally deemed pleasurable to the senses.”
- the fragrance raw materials which comprise the pro-fragrances 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- fragrances described herein are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered. In fact, the tertiary alcohol fragrance raw materials are more suitably delivered by the pro-fragrances of the present invention than by conventional pro- fragrances.
- 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 "Perfumes: Art, Science and Technology”; Miiller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) all of which are incorporated herein by reference.
- pro-fragrances of the present invention are derivatives of substituted and unsubstituted 2-hydroxytetrahydrofuran having the formula:
- R is 2,4-dimethyl-3-cyclo-hexene-l -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), a-3,3- trimethyl-2-norboranylmethyl, 1 , 1 -dimethyl- 1 -(4-methylcyclohex-3-enyl)methyl, 2- phenylethyl, 2-cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 2-(p-methylphenyl)ethyl, 6,6
- Preferred R is 3,7-dimethyl-l,6-octadien-3-ol (linalool, as a racemic mixture or as each optical isomer alone), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol, as a racemic mixture or as each optical isomer alone), and mixtures thereof.
- R 9 is -CHO, -CO 2 M; -CO 2 R 10 , -CONH 2 , -CONHR 10 , -CONRl ⁇ R ⁇ , and mixtures thereof; wherein R ⁇ O and R ⁇ 1 are each independently C1 -C12 linear or branched alkyl, preferably methyl or ethyl; M is hydrogen or a salt forming cation, preferably sodium or potassium; x is an integer from 0 to 19; m) any two R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 units can be taken together to form a fused aromatic or non-aromatic ring comprising from 4 to 7 carbon atoms; n) two or more R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , or R 8 units can be taken together to form a bicyclic, tricyclic, or spir
- R 12 is -SO3M, -OSO3M, -PO3M, -OPO3M, or mixtures thereof; wherein M is hydrogen, one or more salt forming cations sufficient to satisfy charge balance, preferably sodium or potassium; or mixtures thereof; y is an integer from 1 to about 22; p) and mixtures thereof.
- R 12 is -SO3M, -OSO3M, -PO3M, -OPO3M, or mixtures thereof; wherein M is hydrogen, one or more salt forming cations sufficient to satisfy charge balance, preferably sodium or potassium; or mixtures thereof; y is an integer from 1 to about 22; p) and mixtures thereof.
- substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula:
- R ⁇ 3 is hydrogen; R ⁇ is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 10.
- substituted or unsubstituted alkyleneoxyalkyl are defined as moieties having the formula:
- R ⁇ 3 is hydrogen, Ci -Cjg alkyl, C1-C4 alkoxy, and mixtures thereof;
- R* is hydrogen, methyl, ethyl, and mixtures thereof;
- the index x is from 1 to about 9 and the index y is from 1 to about 18.
- substituted or unsubstituted alkylenearyl units are defined as moieties having the formula:
- R ⁇ and R ⁇ 4 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 C1 -Cj2 linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is from 1 to about 14.
- substituted or unsubstituted aryloxy units are defined as moieties having the formula:
- R ⁇ 3 and R ⁇ 4 are each independently hydrogen, hydroxy, C1-C4 alkyl, Cj- C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO2H; -CO2R'; -CONH2; - CONHR'; -CONR*2; wherein R' is C1-C15 linear or branched alkyl), amino, alkylamino, and mixtures thereof.
- substituted or unsubstituted alkyleneoxyaryl units are defined as moieties having the formula:
- R ⁇ 3 and R* 4 are each independently hydrogen, hydroxy, C1 -C4 alkyl, C1 - C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO2H; -CO2R'; -CONH2; - CONHR'; -CONR'2; wherein R' is C ⁇ -C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is from 1 to about 14.
- substituted or unsubstituted oxyalkylenearyl units are defined as moieties having the formula:
- R l 3 and R ⁇ are each independently hydrogen, hydroxy, C1-C4 alkyl, C ⁇ - C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -CO2H; -CO2R'; -CONH2; - CONHR'; -CONR'2; wherein R' is C1-C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, w is from 1 to about 14.
- any two R*, R 2 , R 3 , R 4 , R 7 , 0 r R 8 units can be taken together to form a fused aromatic or non-aromatic ring comprising from 4 to 7 carbon atoms.
- Those skilled in the art will recognize that in the case of fused aromatic rings only one Rl, R 2 , R 3 , R 4 , R5, R6, R 7 ; or R8 um t W JU t ⁇ e present on a carbon atom which is part of an aromatic ring.
- the other Rl, R 2 , R 3 , R 4 , R ⁇ , R ⁇ , R 7 , or R 8 unit will be absent.
- a moiety substituted at a ring carbon may necessitate the use of both substituent groups on a carbon atom to form the moiety.
- both R 3 and R 4 are needed to form an exocyclic double bond as in the general formula:
- any two or more R , R 2 , R 3 , R 4 , R , R , R 7 , or R 8 units can be taken together to form a bicyclic, tricyclic, or spiroannulated ring comprising from 5 to 8 carbon atoms.
- An example in which an Rl and R 7 unit are taken together to form a bicyclo[2.2.2] ring can be depicted by the general formula:
- R , R 2 , R 3 , R 4 , R ⁇ , R6, R 7 , or R 8 units which are on the same ring carbon atom may be taken together to form a spiroannulated ring, an example of which is the tetrahydropyranyl pro-fragrance in which R ⁇ and R" units are taken together to form a cyclohexane ring, having the general formula:
- the pro-fragrances of the present invention release "fragrance raw material alcohols" which provide a pleasurable "fresh” and/or “clean” smell or scent to fabric to which the pro-fragrances are applied.
- 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-l -methanol (Isocyclo geraniol), 4-(l -methylethyl)cyclohexanemethanol (Mayol), a-3,3-trimethyl-2-norborane methanol, l,l-dimethyl-l-(4
- Preferred alcohols released by the compounds 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 (ortho- hawthanol), 2-(m-methylphenyl)ethanol (met ⁇ -hawthanol), 2-(p-methylphenyl)- ethanol (p ⁇ r ⁇ -hawthanol), 2,2-dimethyl-3-(3-methylphenyl)propan-l-ol (majantol), 3-phenyl-2-propen
- fragrance raw materials may be included as either the separate chemical isomer or as the combined racemic mixture.
- fragrance raw materials may be included as either the separate chemical isomer or as the combined racemic mixture.
- 3,7-dimethyl-6-octen-l-ol commonly known by those of ordinary skill in the art as b-citronellol or cephrol, comprises a pair of optical isomers, R-(+)-b-citronellol and S-(-)-b-citronellol.
- Each ofthese materials separately or as a racemic pair are suitable for use as fragrance raw materials in the present invention.
- the tetrahydrofuranyl and tetrahydropyranyl pro-fragrances each will have at least one chiral center which is the C-l carbon contained within the furanyl or pyranyl ring and when taken together with fragrance alcohols having a chiral center, the pro-fragrances of the present invention have the capacity to form diasteriomeric pairs.
- no single isomer or isomer pair is favored over another single isomer or isomer pair, however, if the formulator chooses one isomer or pair of isomers over the other because of their fragrance "character" or other bulk property characteristic, the choice does not diminish the value of the other remaining isomer or isomer pair for the purposes of the present invention.
- the present invention relates to fragrance delivery systems useful in laundry detergent compositions, and rinse-added and dryer-added fabric conditioning compositions.
- the fragrance delivery systems of the present invention provide slow, sustained release of fragrance raw materials which provide the clothing or fabric article with a pleasant "fresh” or “clean” scent.
- the formulator may modify the pyranyl or furanyl portion of the pro-fragrance materials in order to provide increased fabric substantivity or laundry liquor solubility to the compounds which comprise the fragrance delivery system.
- laundry detergent compositions of the present invention which have increased fragrance retention and fragrance longevity, comprise:
- adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach catalysts, bleach activators, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
- non-pyranyl or non-furanyl pro-fragrance materials is defined as other compounds which can suitably release a fragrance raw material, for example, as disclosed in U.S. 5,378,468 Suffis et al., issued January 3, 1995, incorporated herein by reference.
- the rinse added fabric softening compositions of the present invention which have increased fragrance retention and fragrance longevity, comprise:
- compositions optionally from about 0.01% to about 15% by weight, of concentration aids; wherein further said compositions have a pH of less than about 6 at 20 ° C.
- the dryer-added added fabric softening and fabric appearance benefit compositions are delivered by a article of manufacture such as a substrate, preferably a flexible substrate which is added to the dryer, said articles of manufacture comprise:
- a fabric treatment component comprising: a) from about 1 % to about 60% by weight, of a polyamine having the formula; i) a polyamine having a backbone of the formula:
- R is C2-C alkylene, C3-C alkyl substituted alkylene, and mixtures thereof, preferably ethylene, 1 ,2-propylene, 1,3-propylene, more preferably ethylene; ii) a polyamine having a backbone of the formula:
- y is from 5 to about 10,000; and iii) optionally from 0% to 100% of the polyamine backbone NH units are substituted by one or more units having the formula: — (RlO) x R2 wherein Rl is C2-C6 alkylene, C3-C6 alkyl substituted alkylene, and mixtures thereof; R 2 is hydrogen, C1 -C4 alkyl, and mixtures thereof, preferably hydrogen and methyl; wherein m is from 2 to about 700; n is from 0 to about 350; x is from 1 to 12, preferably from 1 to about 4; y is from 5 to 5000.
- 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 1% to about 55%, by weight include the conventional C ⁇ j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the CiQ-Ci secondary (2,3) alkyl sulfates of the formula CH3(CH2) ⁇ (CHOSO 3 " M + ) CH3 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 Ci Q-Ci g alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates), CjQ-Ci alkyl alkoxy carboxylate
- the conventional nonionic and amphoteric surfactants such as the Cj2 _ Ci alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C -C ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines”), Ci Q-Cj amine oxides, and the like, can also be included in the overall compositions.
- the CI Q-CI g N-alkyl polyhydroxy fatty acid amides are highly preferred, especially the Cj2- ⁇ N-methylglucamides. See WO 9,206,154.
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Ci Q-Cjg N-(3-methoxypropyl) glucamide.
- the N-propyl through N-hexyl Ci 2-Cj glucamides can be used for low sudsing.
- C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C]Q-Ci6 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(CHOSO3-M+)(CH 2 )mCH3 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 ⁇ g alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg- C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of C to C 2 alkyl phenols, alkylene oxide condensates of C -C22 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.
- An extensive disclosure ofthese types of surfactants is found in U.S. Pat. 3,929,
- 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:
- R 7 C-N-Q wherein R 7 is C5-C31 alkyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C ⁇ ⁇ -C $ alkyl or alkenyl, or mixtures thereof;
- R 8 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl.
- 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 2 OH, -CH 2 (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 -CH2(CHOH)4CH2OH.
- R 7 CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
- R 8 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-methyl glucomide, a compound of the above formula wherein R 7 is alkyl (preferably C ⁇ ⁇ -C ⁇ ), R 8 , is methyl and Q is 1-deoxyglucityl.
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Ci g-Ci N-(3-methoxypropy ⁇ ) glucamide.
- the N-propyl through N-hexyl C ⁇ -Cjg glucamides can be used for low sudsing.
- C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Ci6 soaps may be used.
- ADJUNCT INGREDIENTS N-alkoxy polyhydroxy fatty acid amides
- 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 surprisingly 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 morphology form of layered silicate.
- SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ +i -y ⁇ 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 amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. 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:
- x is from about 20 to about 30, especially about 27.
- This material is known as Zeolite A.
- the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
- Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
- polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
- Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
- polycarboxylate builders include a variety of categories of useful materials.
- One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in 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-C20 alkyl and alkenyl succinic acids and salts thereof.
- a particularly preferred compound of this type is dodecenylsuccinic acid.
- succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
- Fatty acids e.g., C12-C18 monocarboxylic acids
- the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
- Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
- the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
- Phosphonate builders such as ethane- 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 CJQ-CIO alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
- the CJ Q-C H 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 MgCl2, 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 C 13.15 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 "L ⁇ dige 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 rpm 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 densify 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 “L ⁇ dige Ploughshare” mixer/densifiers are suitable for this process step. Such equipment is typically operated at 40-160 rpm.
- 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 can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e.g. L ⁇ dige CB) to achieve the desired density.
- a moderate speed mixer/densifier e.g. L ⁇ dige KM
- the aforementioned high speed mixer/densifier e.g. L ⁇ dige 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. L ⁇ dige CB) followed by a moderate speed mixer/densifier (e.g. L ⁇ dige KM) to form high density detergent agglomerates.
- a high speed mixer/densifier e.g. L ⁇ dige CB
- a moderate speed mixer/densifier e.g. L ⁇ dige KM
- the 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.
- 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 L ⁇ dige 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. L ⁇ dige KM
- a moderate speed mixer/densifier e.g. L ⁇ dige KM
- compositions of the present invention can contain from about 5% to about 95%, preferably from about 15% to about 90%, more preferably from about 25% to about 85%, and even more preferably from about 25% to about 55%, of biodegradable cationic softener, preferably an ester quaternary ammonium compound (EQA).
- biodegradable cationic softener preferably an ester quaternary ammonium compound (EQA).
- the optional fabric conditioning component is preferably a fabric softening compound which is an ester quaternary ammonium (EQA) compound or its precursor amine having the formula:
- EQA ester quaternary ammonium
- Rl is C ⁇ - C alkyl, C1-C4 hydroxy alkyl group, or benzyl, preferably C1-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; preferably one Rl moiety is a short chain alkyl group, preferably methyl;
- R 2 is Cg-C3Q saturated alkyl or Cg- C30 unsaturated alkyl, Cg-C3o substituted alkyl or Cg-C3 ⁇ - unsubstituted alkyl, preferably C14-C1 g saturated alkyl or C ⁇ -C j g unsaturated alkyl, Ci4-Cj substituted alkyl or C14-C1 g unsubstituted alkyl, more preferably linear Ci4-C ⁇ saturated alkyl, wherein each
- Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials.
- substituents Rl and R 2 of Formula I can optionally be substituted with various groups such as alkoxy 1 or hydroxy 1 groups.
- the preferred compounds can be considered to be diester (DEQA) variations of ditallow dimethyl ammonium methyl sulfate (DTDMAMS), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be EQA monoester (e.g., only one -Y-R 2 group).
- EQA Formula I (wherein all long-chain alkyl substituents are straight-chain): Saturated [C2H5]2 + N[CH2CH2OC(O)C 17 H3 5 ]2 (CH3SO4)-
- biodegradable Formula I compounds suitable for use in the fabric softening compositions herein are:
- a preferred compound is N-methyl, N,N-di-(2-oleyloxyethyl) N-2-hydroxyethyl ammonium methylsulfate.
- R ⁇ is CJ - Cg alkyl or benzyl, preferably Ci -C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; preferably one R* moiety is a short chain alkyl group, preferably methyl;
- R 2 is Cg-C3Q saturated alkyl or Cg-C3Q unsaturated alkyl, Cg- C30 substituted alkyl or C -C3Q unsubstituted alkyl, preferably C14-C1 g saturated alkyl or Ci 4-C] unsaturated alkyl, Cj ⁇ -Cjg substituted alkyl or C ⁇ -Cjg unsubstituted alkyl, more preferably linear C ⁇ -Cj saturated alkyl, wherein each R 2 moiety suitable for use has an Iodine Value of from about 3 to about
- substituents R and R 2 of Formula II can optionally be substituted with various groups such as alkoxyl or hydroxyl groups.
- the preferred ester linked compounds can be considered to be diester variations of ditallow dimethyl ammonium chloride (DTDMAC), which is a widely used fabric softener.
- DTDMAC ditallow dimethyl ammonium chloride
- at least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be DEQA monoester (e.g., only one -Y-R 2 group).
- monoester e.g., only one -Y-R 2 group.
- monoester should be low, preferably less than about 2.5%.
- the level of monoester can be controlled in the manufacturing of the DEQA.
- the quaternary softening compounds with at least partially unsaturated alkyl or acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met. Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used.
- Any reference to IV values hereinafter refers to IV of fatty alkyl or acyl groups and not to the resulting quaternary, e.g., DEQA compound. As the IV is raised, there is a potential for odor problems.
- the optimum storage temperature for stability and fluidity depends on the specific IV of, e.g., the fatty acid used to make DEQA and/or the level/type of solvent selected. Exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/handling of the material in manufacturing operations.
- DEQA Formula II wherein all long-chain alkyl substituents are straight-chain:
- Rl is C1-C4 alkyl, C1-C4 hydroxy alkyl group, preferably methyl; preferably one R moiety is a short chain alkyl group, preferably methyl;
- R 2 is Cg-C3Q saturated alkyl or C -C30 unsaturated alkyl, Cg-C3Q substituted alkyl or C -C3Q unsubstituted alkyl, preferably C ⁇ -Cjg saturated alkyl or C ⁇ A-C ⁇ $ unsaturated alkyl, C ⁇ A-C ⁇ % substituted alkyl or Ci 4-C ⁇ unsubstituted alkyl, more preferably linear C14-C1 g saturated alkyl, wherein each R 2 moiety suitable for use has an Iodine Value of from about 3 to about 60; the counter ion X" is methylsulfate.
- ester quaternary ammonium compound which is suitable for use as a fabric softening compound in the present invention is l,2-bis(tallowyloxy)-3-trimethyl ammoniopropane methylsulfate (DTTMAPMS).
- DTTMAPMS tallowyloxy-3-trimethyl ammoniopropane methylsulfate
- Other suitable examples are l,2-bis(cocoyloxy)-3-trimethyl ammoniopropane methylsulfate, l,2-bis(lauryloxy)-3-trimethyl ammoniopropane methylsulfate, 1,2- bis(oleyloxy)-3-trimethyl ammoniopropane methylsulfate and l,2-bis(stearyloxy)-3- trimethyl ammoniopropane methylsulfate.
- Formula III EQA compounds of this invention are obtained by, e.g., replacing "tallowyl” in the above compounds with, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl” in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs ofthese radicals; replacing "methylsulfate” in the above compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred.
- R* is C1-C4 alkyl or hydroxy alkyl, preferably C1-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl
- R 2 is C -C3Q saturated or unsaturated, substituted or unsubstituted alkyl having an Iodine Value of from about 3 to about 60, preferred R 2 is Cg-Ci4 linear or branched alkyl, more preferred Cg-Cj4 linear alkyl
- R 4 is a C ⁇ - C4 alcohol
- the counter ion, X" can be any softener-compatible anion, preferably methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate, nitrate, benzoate, more preferably methylsulfate.
- the quaternary ammonium compound is a fully saturated compound, such as dimethyl bis(tallowyloxyethyl) ammonium methylsulfate, derived from hardened tallow .
- dimethyl bis(acyloxyethyl) ammonium methylsulfate derivatives of Cg-C3 ⁇ fatty acids such as dimethyl bis(tallowyloxyethyl) ammonium methylsulfate; dimethyl bis(oleyloxyethyl) ammonium methylsulfate or dimethyl bis(cocoyloxyethyl) ammonium methylsulfate.
- the composition of the present invention may comprise from about 15% to about 90% ofthese quaternary ammonium compounds.
- ester quaternary ammonium compounds suitable for use as a fabric softening compound according to the present invention is N-methyl-N,N-bis-(2-C ⁇ 4-C ⁇ g-acyloxy)ethyl-N-2-hydroxyethyl ammonium methylsulfate.
- a preferred example is N-methyl-N,N-bis(2-oleyloxyethyl)-N-(2- hydroxyethyl) ammonium methylsulfate.
- the fabric conditioning composition can be any of those known in the art and/or previously disclosed by others in patent applications. Compositions that are suitable are disclosed in U.S. Pat. Nos.: 3,944,694, McQueary; 4,073,996, Bedenk et al.; 4,237,155, Kardouche; 4,711,730, Gosselink et al.; 4,749,596, Evans et al.; 4,808,086, Evans et al.; 4,818,569, Trinh et al.; 4,877,896, Maldonado et al.; 4,976,879, Maldonado et al.; 5,041,230, Borcher, Sr. et al.; 5,094,761, Trinh et al.; 5,102,564, Gardlik et al.; and 5,234,610, Gardlik et al., all of said patents being incorporated herein by reference.
- the compounds herein can be prepared by standard esterification and quatemization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, incorporated herein by reference.
- the diester quat when specified, it will include the monoester quat that is normally present.
- the percentage of monoester quat should be as low as possible, preferably less than about 20%.
- the level of monoester quat present can be controlled in the manufacturing of the EQA.
- EQA compounds prepared with fully saturated acyl groups are rapidly biodegradable and excellent softeners.
- compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met.
- IV Iodine Value
- Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. As the IV is raised, there is a potential for odor problems.
- Such sources must be deodorized, e.g., by absorption, distillation (including stripping such as steam stripping), etc., as is well known in the art.
- diester compounds derived from fatty acyl groups having low IV values can be made by mixing fully hydrogenated fatty acid with touch hydrogenated fatty acid at a ratio which provides an IV of from about 3 to about 60.
- the polyunsaturation content of the touch hardened fatty acid should be less than about 5%, preferably less than about 1 %.
- touch hardening the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high H2 availability, etc.
- water levels in the raw material must be minimized to preferably less than about 1 % and more preferably less than about 0.5%.
- Storage temperatures should be kept as low as possible and still maintain a fluid material, ideally in the range of from about 49°C to about 75°C.
- the optimum storage temperature for stability and fluidity depends on the specific IV of the fatty acid used to make the diester quaternary and the level/type of solvent selected.
- exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket.
- Adjunct fabric softening compositions employed herein contain as an optional component, at a level of from about 0% to about 95%, preferably from about 20% to about 75%), more preferably from about 20% to about 60%, a carboxylic acid salt of a tertiary amine and/or ester amine which has the formula:
- R ⁇ is a long chain aliphatic group containing from about 8 to about 30 carbon atoms
- R 4 and R ⁇ are the same or different and are independently selected from the group consisting of aliphatic groups containing from about 1 to about 30 carbon atoms, hydroxyalkyl groups of the formula R OH wherein R 8 is an alkylene group of from about 2 to about 30 carbon atoms, and polyalkyleneoxy moieties of the formula R9 ⁇ (R ⁇ ) m - wherein R ⁇ is hydrogen, Cj-C3o alkyl, C1-C30 alkenyl, and mixtures thereof; RlO is ethylene, 1,2 propylene, 1,3-propylene, and mixtures thereof; m is from about 2 to about 10; wherein further the R 4 , R ⁇ , R , R 8 , and R ⁇ chains can be ester interrupted groups; and wherein R 7 is selected from the group consisting of C2-C30 linear alkyl, C2-C30 linear alkenyl, C -C3
- R ⁇ is an aliphatic chain containing from about C12-C3Q linear alkyl
- R6 is C12-C30 linear alkyl
- R 4 is C1-C30 linear alkyl.
- Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallow- dimethylamine, coconutdimethylamine, dilaurylmethylamine, distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-hydroxy- propyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethyl- methylamine, and
- Preferred fatty acids are those wherein R 7 is Cg-C3Q linear alkyl, more preferably Ci 1 -Cj7 linear alkyl.
- Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic acid, 3- chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl)- benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4- hydroxyphenyl)acetic acid, and phthalic acid.
- Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures thereof.
- the amine salt can be formed by a simple addition reaction, well known in the art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980, which is incorporated herein by reference. Excessive levels of free amines may result in odor problems, and generally free amines provide poorer softening performance than the amine salts.
- Preferred amine salts for use herein as optional ingredients are those wherein the amine moiety is a Cg-C3o alkyl or alkenyl dimethyl amine or a di-Cg-C30 alkyl or alkenyl methyl amine, and the acid moiety is a C -C3Q alkyl or alkenyl monocarboxylic acid.
- the amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, since these materials are normally derived from natural fats and oils, or synthetic processed which produce a mixture of chain lengths. Also, it is often desirable to utilize mixtures of different chain lengths in order to modify the physical or performance characteristics of the softening composition.
- Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimethylamine stearate, stearyldimethylamine myristate, stearyldimethylamine oleate, stearyldimethylamine palmitate, distearylmethylamine palmitate, distearylmethylamine laurate, and mixtures thereof.
- a particularly preferred mixture is oleyldimethylamine stearate and distearylmethylamine myristate, in a ratio of 1 : 10 to 10:1, preferably about 1 :1.
- An optional softening agent of the present invention is a nonionic fabric softener material.
- nonionic fabric softener materials typically have an HLB of from about 2 to about 9, more typically from about 3 to about 7.
- the materials selected should be relatively crystalline, higher melting, (e.g., >25 °C).
- the level of optional nonionic softener in the solid composition is typically from about 10% to about 50%, preferably from about 15% to about 40%.
- Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety contains from about 8 to about 30, preferably from about 12 to about 20, carbon atoms.
- such softeners contain from about one to about 3, preferably about 2 fatty acid groups per molecule.
- the polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
- the fatty acid portion of the ester is normally derived from fatty acids having from about 8 to about 30, preferably from about 12 to about 22, carbon atoms. Typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid.
- Highly preferred optional nonionic softening agents for use in the present invention are C10-C26 acyl sorbitan esters and polyglycerol monostearate.
- Sorbitan esters are esterified dehydration products of sorbitol.
- the preferred sorbitan ester comprises a member selected from the group consisting of C10-C26 ac ⁇ l sorbitan monoesters and C10-C26 ac yl sorbitan diesters and ethoxylates of said esters wherein one or more of the unesterified hydroxy 1 groups in said esters contain from 1 to about 6 oxyethylene units, and mixtures thereof.
- sorbitan esters containing unsaturation e.g., sorbitan monooleate
- Sorbitol which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and 1,5- sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No. 2,322,821, Brown, issued June 29, 1943, incorporated herein by reference.)
- sorbitan complex mixtures of anhydrides of sorbitol are collectively referred to herein as "sorbitan.” It will be recognized that this "sorbitan" mixture will also contain some free, uncyclized sorbitol.
- the preferred sorbitan softening agents of the type employed herein can be prepared by esterifying the "sorbitan" mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or fatty acid.
- the esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from such reactions, and the stoichiometric ratios of the reactants can be simply adjusted to favor the desired reaction product.
- etherification and esterification are generally accomplished in the same processing step by reacting sorbitol directly with fatty acids.
- Such a method of sorbitan ester preparation is described more fully in MacDonald; "Emulsifiers:” Processing and Quality Control:, Journal of the American Oil Chemists' Society. Vol. 45, October 1968.
- sorbitan esters herein, especially the "lower” ethoxylates thereof (i.e., mono-, di-, and tri-esters wherein one or more of the unesterified -OH groups contain one to about twenty oxyethylene moieties (Tweens®) are also useful in the composition of the present invention. Therefore, for purposes of the present invention, the term "sorbitan ester" includes such derivatives.
- sorbitan mono-ester e.g., monostearate
- a typical analysis of sorbitan monostearate indicates that it comprises about 27% mono-, 32% di- and 30% tri- and tetra-esters.
- Commercial sorbitan monostearate therefore is a preferred material.
- Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10:1 and 1 :10, and 1,5- sorbitan esters are useful. Both the 1,4- and 1,5-sorbitan esters are useful herein.
- alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters.
- Such mixtures are readily prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly the 1,4- and 1,5-sorbitans, with the corresponding acid, ester, or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials prepared in this manner will comprise mixtures usually containing minor proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and the like. In the present invention, it is preferred that such impurities are present at as low a level as possible.
- the preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of the C20-C26' an d higher, fatty acids, as well as minor amounts of Cg, and lower, fatty esters.
- Glycerol and polyglycerol esters are also preferred herein (e.g., polyglycerol monostearate with a trade name of Radiasurf 7248).
- Glycerol esters can be prepared from naturally occurring triglycerides by normal extraction, purification and/or inter-esterification processes or by esterification processes of the type set forth hereinbefore for sorbitan esters. Partial esters of glycerin can also be ethoxylated to form usable derivatives that are included within the term "glycerol esters.”
- Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.
- the "glycerol esters” also include the polyglycerol, e.g., diglycerol through octaglycerol esters.
- the polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages.
- the mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
- the dryer activated fabric softening compositions of the present invention may further includes a co-softener.
- the co-softener may comprise a carboxylic acid salt of a tertiary amine, tertiary amine ester, or mixtures thereof.
- the carboxylic acid salt forming anion moiety of the co-softener may be selected from the group consisting of lauric, myristic, palmitic, stearic, oleic and mixtures thereof.
- the amine salt of the co-softener may be selected from the group consisting of oleyldimethylamine stearate, dioleylmethylamine stearate, linoleyldimethylamine stearate, dilinoleylmethylamine stearate, stearyldimethylamine stearate, distearylmethylamine myristate, stearyldimethylamine palmitate, distearylmethylamine palmitate, distearylmethylamine myristate, distearylmethylamine palmitate, distearylmethylamine laurate, dioleyldistearylmethylamine oleate, distearylmethylamine oleate, and mixtures thereof.
- the products herein can also contain from about 0.5% to about 60%, preferably from about 1% to about 50%, cyclodextrin/perfume inclusion complexes and/or free perfume, as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al., issued Aug. 18, 1992; and 5,234,610, Gardlik et al., to issue Aug. 10, 1993, which are incorporated herein by reference.
- Perfumes are highly desirable, can usually benefit from protection, and can be complexed with cyclodextrin.
- Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective.
- perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos.: 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference. Many of the art recognized perfume compositions are relatively substantive to maximize their odor effect on substrates. However, it is a special advantage of perfume delivery via the perfume/cyclodextrin complexes that nonsubstantive perfumes are also effective.
- Stabilizers can be present in the compositions of the present invention.
- the term "stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.05% to about 0.1% for antioxidants and more preferably from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions for the compositions. Use of antioxidants and reductive agent stabilizers is especially advantageous for low scent products (low perfume).
- antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-l; a mixture of BHT, BHA, propyl gallate, and citric acid available from Eastman Chemicals Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane ® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-l/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA.
- reductive agents examples include sodium borohydride, hypophosphorous acid, and mixtures thereof.
- the present invention can include other adjunct components (minor components) conventionally used in textile treatment compositions, for example, colorants, perfumes, perfume systems, preservatives, optical brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, anti- wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti- corrosion agents, antifoam agents, and the like.
- adjunct components for example, colorants, perfumes, perfume systems, preservatives, optical brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, anti- wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti- corrosion agents, antifoam agents, and the like.
- 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.
- reaction vessel The contents of the reaction vessel is transferred to a separatory funnel, diluted with diethyl ether (150 mL), extracted with sat. NaCl and the organic phase is dried over MgSO4. The solvent is removed in vacuo and the resulting oil is purified by passing the crude material over silica gel and eluting with petroleum ether/2% ethyl acetate to yield a colorless oil.
- reaction vessel The contents of the reaction vessel is transferred to a separatory funnel, diluted with diethyl ether (150 mL), extracted with sat. NaCl, then washed with water, and the organic phase is dried over MgSO4. The solvent is removed in vacuo and the resulting oil is purified by passing the crude material over silica gel and eluting with petroleum ether/2% ethyl acetate to yield a colorless oil.
- 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.
- 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 pro-fragrances of the present invention.
- EXAMPLE 14 The following is an example of a solid bleaching compositon which comprises a pro-fragrance according to the present invention.
- EXAMPLE 15 The following is an example of a liquid bleaching composition comprising a pro-accord of the present invention. TABLE IV
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002295110A CA2295110A1 (en) | 1997-06-27 | 1998-06-26 | Pro-fragrance cyclic acetals |
JP50575299A JP2002507212A (en) | 1997-06-27 | 1998-06-26 | Pro-aromatic cyclic acetal |
EP98931617A EP0991635A1 (en) | 1997-06-27 | 1998-06-26 | Pro-fragrance cyclic acetals |
BR9810946-4A BR9810946A (en) | 1997-06-27 | 1998-06-26 | "cyclic acetals for fragrance" |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5116897P | 1997-06-27 | 1997-06-27 | |
US60/051,168 | 1997-06-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999000377A1 true WO1999000377A1 (en) | 1999-01-07 |
Family
ID=21969746
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/013278 WO1999000377A1 (en) | 1997-06-27 | 1998-06-26 | Pro-fragrance cyclic acetals |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0991635A1 (en) |
JP (1) | JP2002507212A (en) |
CN (1) | CN1268127A (en) |
AR (1) | AR013142A1 (en) |
BR (1) | BR9810946A (en) |
CA (1) | CA2295110A1 (en) |
WO (1) | WO1999000377A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7980001B2 (en) * | 2004-02-27 | 2011-07-19 | The Procter & Gamble Company | Fabric conditioning dispenser and methods of use |
WO2014202416A1 (en) * | 2013-06-17 | 2014-12-24 | Firmenich Sa | Compounds for a controlled release of active molecules |
WO2016049523A1 (en) * | 2014-09-25 | 2016-03-31 | International Flavors & Fragrances Inc. | High-coverage, low odor malodor counteractant compounds and methods of use |
US10160969B2 (en) | 2014-01-16 | 2018-12-25 | Wave Life Sciences Ltd. | Chiral design |
US10167309B2 (en) | 2012-07-13 | 2019-01-01 | Wave Life Sciences Ltd. | Asymmetric auxiliary group |
US10280192B2 (en) | 2011-07-19 | 2019-05-07 | Wave Life Sciences Ltd. | Methods for the synthesis of functionalized nucleic acids |
US10307434B2 (en) | 2009-07-06 | 2019-06-04 | Wave Life Sciences Ltd. | Nucleic acid prodrugs and methods of use thereof |
US10329318B2 (en) | 2008-12-02 | 2019-06-25 | Wave Life Sciences Ltd. | Method for the synthesis of phosphorus atom modified nucleic acids |
US10428019B2 (en) | 2010-09-24 | 2019-10-01 | Wave Life Sciences Ltd. | Chiral auxiliaries |
WO2021160670A1 (en) | 2020-02-13 | 2021-08-19 | Glycoscience, S.L. | 3'-ketoglycoside compound for the slow release of a volatile alcohol |
WO2023099327A1 (en) | 2021-11-30 | 2023-06-08 | Glycoscience, S.L. | Slow-release formulation |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106188172A (en) * | 2016-07-13 | 2016-12-07 | 上海应用技术学院 | A kind of glucoside compounds with Lignum Santali Albi fragrance and preparation method thereof |
CN107325273B (en) * | 2017-06-22 | 2019-09-20 | 温州大学 | High molecular polymer and preparation method thereof and application in acid-sensitive type amphiphilic nano micella |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3624106A (en) * | 1970-04-06 | 1971-11-30 | Wayne I Fanta | Tetrahydropyranyl ether of 3-endo-methyl-3-exo(4{40 -methyl-5{40 -hydroxypentyl) norcamphor |
DE2047030A1 (en) * | 1968-09-27 | 1972-03-30 | Unilever N V , Rotterdam (Nieder lande) | Detergents |
EP0155002A2 (en) * | 1984-03-14 | 1985-09-18 | Kuraray Co., Ltd. | Hydroformylation of 3-methyl-3-buten-1-ol and use of such hydroformylation products |
WO1996012785A1 (en) * | 1994-10-20 | 1996-05-02 | The Procter & Gamble Company | Fabric softener compositions with reduced environmental impact |
WO1997016522A1 (en) * | 1995-11-03 | 1997-05-09 | The Procter & Gamble Company | Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity |
WO1997042290A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Polyamines having fabric appearance enhancement benefits |
-
1998
- 1998-06-26 CA CA002295110A patent/CA2295110A1/en not_active Abandoned
- 1998-06-26 JP JP50575299A patent/JP2002507212A/en active Pending
- 1998-06-26 EP EP98931617A patent/EP0991635A1/en not_active Withdrawn
- 1998-06-26 WO PCT/US1998/013278 patent/WO1999000377A1/en not_active Application Discontinuation
- 1998-06-26 BR BR9810946-4A patent/BR9810946A/en not_active IP Right Cessation
- 1998-06-26 CN CN 98808557 patent/CN1268127A/en active Pending
- 1998-06-26 AR ARP980103114 patent/AR013142A1/en not_active Application Discontinuation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2047030A1 (en) * | 1968-09-27 | 1972-03-30 | Unilever N V , Rotterdam (Nieder lande) | Detergents |
GB1277135A (en) * | 1968-09-27 | 1972-06-07 | Unilever Ltd | Detergent compositions |
GB1342014A (en) * | 1968-09-27 | 1973-12-25 | Unilever Ltd | Detergent compositions |
US3624106A (en) * | 1970-04-06 | 1971-11-30 | Wayne I Fanta | Tetrahydropyranyl ether of 3-endo-methyl-3-exo(4{40 -methyl-5{40 -hydroxypentyl) norcamphor |
EP0155002A2 (en) * | 1984-03-14 | 1985-09-18 | Kuraray Co., Ltd. | Hydroformylation of 3-methyl-3-buten-1-ol and use of such hydroformylation products |
WO1996012785A1 (en) * | 1994-10-20 | 1996-05-02 | The Procter & Gamble Company | Fabric softener compositions with reduced environmental impact |
WO1997016522A1 (en) * | 1995-11-03 | 1997-05-09 | The Procter & Gamble Company | Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity |
WO1997042290A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Polyamines having fabric appearance enhancement benefits |
Non-Patent Citations (1)
Title |
---|
V. BOLITT ET AL.: "Triphenylphosphine Hydrobromide: A Mild and Efficient Catalyst for Tetrahydropyranylation of Tertiary Alcohols", TETRAHEDRON LETTERS, vol. 29, no. 36, 1988, OXFORD GB, pages 4583 - 4586, XP002081001 * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7980001B2 (en) * | 2004-02-27 | 2011-07-19 | The Procter & Gamble Company | Fabric conditioning dispenser and methods of use |
US10329318B2 (en) | 2008-12-02 | 2019-06-25 | Wave Life Sciences Ltd. | Method for the synthesis of phosphorus atom modified nucleic acids |
US10307434B2 (en) | 2009-07-06 | 2019-06-04 | Wave Life Sciences Ltd. | Nucleic acid prodrugs and methods of use thereof |
US10428019B2 (en) | 2010-09-24 | 2019-10-01 | Wave Life Sciences Ltd. | Chiral auxiliaries |
US10280192B2 (en) | 2011-07-19 | 2019-05-07 | Wave Life Sciences Ltd. | Methods for the synthesis of functionalized nucleic acids |
US10167309B2 (en) | 2012-07-13 | 2019-01-01 | Wave Life Sciences Ltd. | Asymmetric auxiliary group |
US9550960B2 (en) | 2013-06-17 | 2017-01-24 | Firmenich Sa | Compounds for a controlled release of active molecules |
WO2014202416A1 (en) * | 2013-06-17 | 2014-12-24 | Firmenich Sa | Compounds for a controlled release of active molecules |
US10590365B2 (en) | 2013-06-17 | 2020-03-17 | Firmenich Sa | Compounds for a controlled release of active molecules |
US10160969B2 (en) | 2014-01-16 | 2018-12-25 | Wave Life Sciences Ltd. | Chiral design |
EP3197421A4 (en) * | 2014-09-25 | 2018-03-28 | International Flavors & Fragrances Inc. | High-coverage, low odor malodor counteractant compounds and methods of use |
WO2016049523A1 (en) * | 2014-09-25 | 2016-03-31 | International Flavors & Fragrances Inc. | High-coverage, low odor malodor counteractant compounds and methods of use |
US10549006B2 (en) | 2014-09-25 | 2020-02-04 | International Flavors & Fragrances Inc. | High-coverage, low odor malodor counteractant compounds and methods of use |
WO2021160670A1 (en) | 2020-02-13 | 2021-08-19 | Glycoscience, S.L. | 3'-ketoglycoside compound for the slow release of a volatile alcohol |
WO2023099327A1 (en) | 2021-11-30 | 2023-06-08 | Glycoscience, S.L. | Slow-release formulation |
Also Published As
Publication number | Publication date |
---|---|
AR013142A1 (en) | 2000-12-13 |
CA2295110A1 (en) | 1999-01-07 |
EP0991635A1 (en) | 2000-04-12 |
CN1268127A (en) | 2000-09-27 |
JP2002507212A (en) | 2002-03-05 |
BR9810946A (en) | 2000-09-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6395695B1 (en) | Pro-fragrance linear acetals and ketals | |
EP0922084B1 (en) | Laundry detergent compositions comprising beta-ketoester pro-fragrances | |
US6165953A (en) | Dryer added fabric softening compositions and method of use for the delivery of fragrance derivatives | |
US6147037A (en) | Fragrance delivery systems | |
WO1999000377A1 (en) | Pro-fragrance cyclic acetals | |
CZ47999A3 (en) | Textile attenuating agents supplied during mixing and textile treatment process | |
US6177389B1 (en) | Detergent compositions comprising orthocarbonate pro-fragrances | |
US6150310A (en) | Laundry detergent compositions comprising β-ketoester pro-fragrances | |
WO1998047996A1 (en) | Laundry detergent compositions comprising fragrance pro-accords | |
CA2307892A1 (en) | Laundry compositions having reduced malodor and methods for providing the same | |
MXPA00000125A (en) | Pro-fragrance linear acetals and ketals | |
MXPA00000126A (en) | Pro-fragrance cyclic acetals | |
MXPA00004211A (en) | Laundry compositions having reduced malodor and methods for providing the same | |
MXPA99001727A (en) | Hand-wash laundry detergent compositions comprising beta-ketoester pro-fragrances | |
MXPA99001778A (en) | LAUNDRY DETERGENT COMPOSITIONS COMPRISING&bgr;-KETOESTER PRO-FRAGRANCES | |
MXPA99001668A (en) | Fragrance delivery system for liquid detergent compositions | |
MXPA99001528A (en) | Rinse added fabric softening compositions and method of use for the delivery of fragrance precursors |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 98808557.7 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): BR CA CN JP MX NO US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2295110 Country of ref document: CA Ref document number: 2295110 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1998931617 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2000/000126 Country of ref document: MX |
|
WWP | Wipo information: published in national office |
Ref document number: 1998931617 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09445324 Country of ref document: US |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1998931617 Country of ref document: EP |