Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/10—Washing or bathing preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/507—Compounds releasing perfumes by thermal or chemical activation

Definitions

• the present invention relates to a pro-fragrance silicone polymer and compositions thereof, more specifically a pro-fragrance silicone polymer derived from an aminoalkyl polysiloxane and a fragrance carbonyl compound.
• Silicone polymers are widely known and have been used for providing softness and smoothness to a surface, e.g., of skin, textile fibers, tissues, and hair.
• a surface e.g., of skin, textile fibers, tissues, and hair.
• One area is for surface treating to provide softness to materials such as fibers, tissues, or clothes as pre-treating agent.
• Conventional silicone polymers are also used in various products, e.g., cleaning or laundry detergents, fabric softeners, shampoos, hair conditioner, which are applied later during process of washing, for maintaining softness of materials such as fabrics and hair.
• such products containing silicone polymers tend to be used on a daily basis to maintain softness or provide further softness to fabrics and/or hair.
• Aminoalky polysiloxanes are one type of conventional silicone polymer employed as a softening agent in applications for washing; for example, detergent, fabric softener, and the like. Such amino polysiloxanes can be formulated alone or in combination with any materials commonly used in laundry products, e.g., surfactants such as anionic, cationic, and nonionic surfactants and polyurethane in compositions. See Japan publication (KOKAI) H8-325952, issued December 10, 1996, and Japan patent publication (KOKAI) H8-246354, issued September 24, 1996, and U.S. Patent 5,591 ,880 to Anthony J. O'Lenick, Jr, issued January 7, 1997.
• One class of amino polysiloxanes having an alkylene moiety is disclosed to provide improved dispersion in addition to softness to fabrics. See U.S. Patent 5,378,787 to Vrckovnik et al., issued January 3, 1995. Due to deposition property of silicone polymers to maintain softness of fabric and the hair, these silicone polymers are formulated into applications such as detergents and softeners for daily washing in addition to pre-treatment.
• V ⁇ (CH 2 ) e -N C— W
• P has a first and a second randomly repeating monomer unit, wherein the first randomly repeating monomer unit is
• Q is oxygen, sulfur, or -NH-.
• V and W are independently hydrogen; or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons.
• R1 , R2, R , R4 R5 R6_ anc j R7 are independently hydrocarbons of 1 to about 10 carbons or a phenyl; m is an integer of 0 to about 500; n is an integer of 0 to about 100; the sum of m and n is an integer of at least 1 ; a is an integer of 1 to about 20; b is an integer of 1 to about 20; c is an integer of 0 to about 100; d is an integer of 1 to about 20; e is an integer of 1 to about 20; f is an integer of 1 to about 20; g is an integer of 1 to about 100; h is an integer of 1 to about 20; j is an integer of 1 to about 20; and k is an integer of 1 to about 20.
• pro-fragrance silicone polymer means a component that is converted into an active fragrance for providing desirable odor by chemical breakdown of the component; e.g., by hydrolysis.
• schiff base refers to a class of unit obtained by chemical reaction (e.g., condensation, dehydration) from an aldehyde or a ketone with primary amines.
• silicone polymer means a polymer which contains - Si(R) 2 -O- repeating units in the backbone.
• the silicone polymer includes a component called “polysiloxane” and “siloxane.”
• aminoalkyl polysiloxane is a polymer which contains -Si(R) 2 -O- repeating units and at least one aminoalkyl substituent of -R-NH 2 in terminal or branched position.
• carbonyl compound means a compound which has at least one carbonyl unit of -CO-, including aldehydes, ketones, and carboxylic acids having -COOR unit; preferably, aldehydes or ketones.
• hydrocarbon means an organic compound consisting of carbon and hydrogen, and is straight, branched, or cyclic, saturated or unsaturated; in certain embodiments the hydrocarbon may also include one or more oxygen atoms.
• alkyl means a carbon-containing chain, which may be straight, branched, or cyclic; saturated or unsaturated; and substituted (mono- or poly-) or unsubstituted.
• alkoxyl means -O-R, wherein R is alkyl, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy.
• the present invention relates to a pro-fragrance silicone polymer comprising the following structure:
• X, Y, and Z are independently the following:
• -P ⁇ (CH 2 )h-N C-W V (IV); or iv. a hydrocarbons of 1 to about 10 carbons or a phenyl, wherein at least one of X, Y, and Z are formula (II), (III), or (IV).
• P has a first and a second randomly repeating monomer unit (hereinafter "RRMU"), wherein the first RRMU is
• Q is oxygen, sulfur, or -NH-.
• V and W are independently hydrogen; or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrocarbons of 1 to about 10 carbons or a phenyl;
• m is an integer of 0 to about 500;
• n is an integer of 0 to about 100; the sum of m and n is an integer of at least 1 ;
• a is an integer of 1 to about 20;
• b is an integer of 1 to about 20;
• c is an integer of 0 to about 100;
• d is an integer of 1 to about 20;
• e is an integer of 1 to about 20;
• f is an integer of 1 to about 20;
• g is an integer of 1 to about 100;
• h is an integer of 1 to about 20;
• j is an integer
• X, Y, and Z are the same or different from one another selected from the group consisting of the following formula:
• -(CH 2 )h-N C- ⁇ w V (IV); or iv. a hydrocarbons of 1 to about 10 carbons or a phenyl, wherein at least one of X, Y, and Z are formula (II), (III), or (IV).
• P has a first and a second RRMU, wherein the first RRMU is
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 of the above structure (I) are the same and are an alkyl of 1 to about 10 carbons or a phenyl. More preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are methyl or phenyl.
• X and Y are the same or different and are formula (II), (III), (IV), or hydrocarbons of 1 to about 10 carbons or phenyl.
• X and Y are formula (II) or a hydrocarbon of 1 to about 10 carbons or a phenyl.
• at least one of X and Y are preferably formula (II), (III), or (IV).
• Z and the remainder of X and Y are preferably a hydrocarbon of 1 to about 10 carbons or a phenyl.
• Z is formula (II), (III), or (IV) when X and Y are hydrocarbons of 1 to about 10 carbons or phenyl; more preferably X and Y are the same.
• Z can be formula (II), when X and Y are the same, preferably formula (II).
• V and W of (II), (III), and (IV) can be independently hydrogen; or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons.
• V and W of (II), (III), and (IV) herein are preferably derived from a fragrance carbonyl compound, preferably an aldehyde of a ketone.
• a fragrance carbonyl compound preferably an aldehyde of a ketone.
• one of W and V are hydrogen and the remainder is a hydrocarbon of 1 to about 30 carbons that can include alkyl, alkenyl, or aryl moieties.
• V and W are derived from ketones, both V and W are preferably hydrocarbons of 1 to about 30 carbons.
• V and W can be bonded together to form a ring.
• the fragrance carbonyl compound is a cyclic carbonyl compound.
• the sum of V and W contains 1 to about 50 carbons.
• the pro-fragrance silicone polymer can include two of formula (II) substituents.
• X and Y are suitable positions (terminal position) to substitute formula (II).
• Z is methyl or phenyl.
• a preferred embodiment is the following (structure (V)):
• W-C N-(CH 2 ) b Q-(CH 2 ) a Usi- ⁇ si- ⁇ Hs ⁇ - ⁇ Usi (CH 2 ) a -Q -(CH 2 ) b -N-C-W ( s I l J J CC I I J r mr ⁇ I J n I L J r- ' V v I
• V and W are hydrogen or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons; m is an integer of 0 to about 500; and n is an integer of 1 to about 100.
• Some specific examples of the present pro-fragrance silicone polymer having structure (V) useful herein include, but are not limited to;
• CH 3 CH which are derived from 2,4-dimethyl-3-cyclohexyl carboxyaldehyde and aminopropyl polysiloxane.
• pro-fragrance silicone polymer having formula (II) at position Z of structure (I) is the following (structure VI):
• X and Y are the same or different methyl or phenyl; V and W are hydrogen or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons; m is an integer of 0 to about 500; and n is an integer of 1 to about 100.
• pro-fragrance silicone polymers having the structure (VI) are nonlimitingly illustrated by the following:
• n is integer from 2 to about 6.
• the pro-fragrance silicone polymer is a highly branched compound having the following structure:
• V and W are hydrogen or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons; m is an integer of 0 to about 500; and n is an integer of 1 to about 100.
• the pro-fragrance silicone polymer of the present invention includes the following (structure VIII):
• V and W are hydrogen or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 carbons; m is an integer of 0 to about 500; and n is integer of 0 to about 100.
• the pro-fragrance silicone polymer of the present invention is derived from an aminoalkyl polysiloxane and a fragrance carbonyl compound by condensation which produces a schiff base unit.
• fragrance sources of the pro-fragrance silicone polymer produce a pleasant fragrance.
• a silicone polymer e.g., aminoalkyl polysiloxane
• Most of the pleasing smell is produced by hydrolysis of schiff base moiety of the pro-fragrance silicone polymer rather than provide good fragrance in a non-hydrolyzed state. Consequently, the pro- fragrance silicone polymer herein releases a pleasant fragrance by hydrolysis. Hydrolysis is a chemical reaction against condensation or dehydration.
• the mechanism of hydrolysis generally proceeds against steps of condensation on a reactive center.
• Such hydrolysis herein, is caused on the schiff base of structure (I) which is prepared by an aminoalkyl polysiloxane and a fragrance carbonyl compound.
• the schiff base of the pro-fragrance silicone polymer tends to be hydrolyzed by humidity and sweat when the pro-fragrance when depositing to the fabric and the hair.
• the hydrolysis of the pro-fragrance silicone polymer herein can be characterized by a half-life less than 60 minutes when measured at pH 0 by the Hydrolysis Half-life (t-1/2) Test as described herein.
• the pro-fragrance silicone polymers of the present invention are stable under pH conditions encountered in the formulation and storage of products containing the pro-fragrance silicone (e.g., laundry detergents, fabric softeners, shampoos, hair conditioners) which have a pH of from about 7.1 to about 13, and during solution-use of such products. Due to hydrophilicity and high degree of heteroatom incorporation, these pro-fragrance compounds give reasonably good deposition from e.g., a laundering solution onto fabrics (or lathering solution to hair.) Because the pro-fragrance silicone polymers are subject to hydrolysis when the pH is reduced, they are hydrolyzed to release fragrance carbonyl compound when the fabrics (or other surface) upon which they have been deposited are exposed even to reduced pH such as is present in rinse water and humidity. Such a reduction in pH is preferably at least about 0.1 , more preferably 12
• the pH is reduced by at least about 0.5 units to a pH of about 7.5 or less, more preferably about 6.9 or less.
• the solution in which the fabric (or other surface) is washed is alkaline.
• the pro-fragrance silicone polymer of the present invention may be further designed to readily disperse in aqueous solution and thereby result in reasonably good deposition, e.g., from laundering solution onto fabric.
• the pro-fragrance silicone polymer of the present invention can be derived from an aminoalkyl polysiloxane and a fragrance carbonyl compound by condensation.
• the aminoalkyl polysiloxane of the present invention can include any component which provides softening efficacy to, e.g., fabric or hair.
• the aminoalkyl polysiloxane useful herein also can provide durability, wrinkle control, and water dispersability, along with softening to the fabrics and the hair.
• laundry detergents for fabrics; softeners for fabrics or textile fibers, cleaning products for the hair or the skin are useful.
• Such known aminoalkyl polysiloxane that can provide the pro-fragrance silicone polymer of the present invention are commercially available as an amino- denatured silicone polymer.
• Such amino-denatured pro-fragrance silicone polymers include tradename DMS-A11 , DMS-A12, DMS-A15, DMS-A21 , DMS- A32, AMS-132, AMS-152, AMS-162, AMS-233, ATM-1112, and ATM-1322, supplied by Gelest, Inc.
• Fragrance carbonyl compounds useful herein derives the pro-fragrance silicone polymer of the present invention. 13
• the fragrance carbonyl compound can be saturated, unsaturated, linear, branched, or cyclic, preferably C7 or higher unsaturated.
• the formulae of the fragrance carbonyl compound can include alkyl, alkenyl, or aryl moieties.
• the carbonyl compound can further include those having additional functional groups such as alcohols, esters, or ethers as well.
• the fragrance carbonyl compound include a fragrance aldehyde or a fragrance ketone, conventionally used for condensation, for example, a pro-fragrance schiff base formation.
• Preferred fragrance aldehyde useful herein include an aliphatic aldehyde, a terpenic aldehyde, and an aromatic aldehyde.
• Nonlimiting examples of the aliphatic aldehyde include hexyl aldehyde (caproaldehyde), heptyl aldehyde, octyl aldehyde (caprylaldehyde), nonyl aldehyde (pelargonaldehyde), decyl aldehyde (capraldehyde), undecyl aldehyde, dodecyl aldehyde (lauric aldehyde), tridecyi aldehyde, 3,5,5-trimethylhexanal, 2- methyldecanal (methyloctylacetaldehyde), 2-methylundecanal
• terpenic aldehyde useful for the pro-fragrance silicone polymer herein include 3,7-dimethyl-7-methoxyoctan-1-al
• the preferred fragrance ketone useful herein include an aliphatic ketone, a terpenic and sesquiterpenic ketone, a cyclic ketone, or an aromatic ketone.
• the ketones can be saturated, unsaturated, linear, branched, or cyclic, preferably including alkyl, alkenyl, or aryl moieties.
• the ketones can include other functional groups such as ethers or esters.
• Nonlimiting examples of the aliphatic ketone includes 3-hydroxy-2- butanone (acetoine), 2,3-butanedione (diacetyl), 2-heptanone (methyl amyl ketone), 3-octanone (ethyl amyl ketone), 2-octanone (methyl hexyl ketone), 2- undecanone (methyl nonyl ketone), 6-methyl-5-hepten-2-one, acetyl diisoamylene (koavone).
• Examples of the terpenic and sesquiterpenic ketone includes 1 ,7,7- trimethyl bicyclo[2.2.1]heptan-2-one (camphor), 1 ,8-p-menthadien-6-one (carvone), p-menthan-3-one (menthone), d-p-menth-4(8)-en-3-one ( -pulegone), p-menth-1-en-3-one (piperitone), 1 ,3,3-trimethyl-bicyclo[2.2.1]heptan-2-one (fenchone), 6,10,-dimethyl-5,9-undecadiene-2-one (geranyl acetone), acetyl cedrene (cedryl methyl ketone), 5,6-dimethyl-8-isopropenylbicyclo-[4.4.0]-1- decen-3-one (nootkatone), 4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one ( ⁇
• cyclic ketone examples include 3-hydroxy-2-methyl-4/-/-pyran-4-one (maltol), 2-ethyl-3-hydroxy-4/-/-pyran-4-one (ethyl maltol), 2,5-diemthyl-4-hydroxy- 2/-/-furan-3-one, 4,5-dimethyl-3-hydroxy-5H-furan-2-one (sugar lactone), p-t- butylcyclohexanone, 2-amylcyclopentanone, 2-heptylcyclopentanone, 3-methyl- 2-pentyl-2-cyclopenten-1 -one (dihydrojasmone), 3-methyl-2-(2-cis-penten-1 -yl)-2- cyclopenten-1-one (c/s-jasmone), 6 (or 7)-ethylidene-octahydro-5,8-methano-2H- benzopyrane (florex), 7-methyl-octahydro-1 ,4
• aromatic ketone examples include, acetophenone (methyl phenyl ketone), p-methyl acetophenone (p-tolyl methyl ketone), benzyl acetone, 7- methyl-3,4-dihydro-(2H)-1 ,5-benzodioxepin-3-one (calone), 4-(4-hydroxyphenyl)- 2-butanone (raspberry ketone), p-methoxyphenylbutanone (anisyl acetone), 4-(4- hydroxy-3-methoxyphenyl)-2-butanone (Zingerone), 2-acetonaphthone (methyl ⁇ - naphthyl ketone), 4-phenyl-4-methyl-2-pentanone, and benzophenone (diphenyl ketone).
• acetophenone methyl phenyl ketone
• p-methyl acetophenone p-tolyl methyl ketone
• ketones include Ethyl ketopropinate (ethyl pyruvate), isoamyl ketopropionate (isoamyl pyruvate), ethyl acetoacetate, ethyl ⁇ - ketovalerate (ethyl levulinate), methyl jasmonate, and methyl dihydrojasmonate.
• Ethyl ketopropinate ethyl pyruvate
• isoamyl ketopropionate isoamyl pyruvate
• ethyl acetoacetate ethyl ⁇ - ketovalerate (ethyl levulinate)
• methyl jasmonate methyl dihydrojasmonate
• the pro-fragrance silicone polymer of the present invention can be prepared by any method used for achieving a conventional condensation reaction, e.g., Dean-Stark method with the acid-catalyzed reaction of an aldehyde and an amine, preferably the primary amine.
• a conventional condensation reaction e.g., Dean-Stark method with the acid-catalyzed reaction of an aldehyde and an amine, preferably the primary amine.
• fragrance silicone polymer preferably an aminoalkyl polysiloxane is prepared as the primary amine.
• the reaction can generally proceed under a catalyst and solvent.
• the preferred catalyst is a Lewis acid.
• Exemplary acidic catalysts are p-toluene sulfonic acid, methane sulfonic acid, sulfuric acid, hydrochloric acid, sulfosalicylic acid, and mixtures thereof or supported sulfonic acid catalysts, e.g., AMBERLYST 15TM.
• acid catalysts with pKa's among 3 and 4 are the most desirable to minimize unnecessary side-reaction.
• Non-acidic catalysts are useful in the present invention. Examples are Girder KSF, boron trifluoride etherate, potassium hydrogen sulfate, copper sulfate, and ion excharger.
• the solvent useful herein can be any solvent used in the conventional condensation or dehydration by Dean-Stark apparatus, which has sufficient stability during the process.
• "Sufficient stability” herein means a solvent which does not cause decomposition or degradation as a side-reaction during the heating step.
• the preferred solvent is hexane, benzene, or toluene. See Meskens, F., Synthesis, (7) 501 (1981) and Meskens, F., Jannsen Chim Ada (1) 10 (1983), Bunton, CA. et al, J. Org. Chem. (44), 3238, (1978), and Cort, O., et al, J. Org. Chem. (51), 1310 (1986, Meskens, F., Synthesis, (7), 501 , (1981) and Lu, T.-J, et al. J. Org. Chem. (60), 2931 , (1995).
• a preferred method of making the pro-fragrance silicone polymer of the present invention includes the steps of (a) adding the aminoalkyl polysiloxane and the fragrance carbonyl compound to a environment wherein the carbonyl compound is selected from the group consisting of an aldehyde, a ketone, and mixtures thereof; and (b) pressurizing the mixture of step (a), wherein the pressu zation causes the fragrance carbonyl compound and the aminoalkyl polysiloxane to react and form the pro-fragrance silicone polymer.
• pressurizing means changing any condition of the reaction for deriving the pro- fragrance silicone polymer from the aminoalkyl polysiloxane and the fragrance carbonyl compound, by increasing the temperature.
• Pressurizing herein includes the conditions produced by physically decreasing the volume by pressure, filling the environment with a gas stream which provides high pressure, and heating; preferably the pressuhzation herein is achieved by heating.
• step (a) further comprises adding a catalyst, solvent, a dehydrating agent, or mixtures 17
• the preferred solvent is hexane, benzene, or toluene.
• the catalyst useful herein includes an acidic catalysts (e.g., p-toluene sulfonic acid, methane sulfonic acid, sulfu c acid, hydrochloric acid, and sulfosalicylic acid preferably) and non-acidic catalysts (e.g., Girder KSF, boron trifluoride etherate, potassium hydrogen sulfate, copper sulfate, and ion excharger), preferably a Lewis acid.
• an acidic catalysts e.g., p-toluene sulfonic acid, methane sulfonic acid, sulfu c acid, hydrochloric acid, and sulfosalicylic acid preferably
• non-acidic catalysts e.g., Girder KSF, boron trifluoride etherate, potassium hydrogen s
• Hydrolysis half-life is the measurement used to determine the ease with which the pro-fragrance silicone polymer undergoes acid hydrolysis and thereby releases fragrance component(s) upon exposure to acid conditions.
• the pro- fragrance silicone polymer of the present invention preferably has a half-life of less than 60 minutes, under the described hydrolysis conditions at pH 0; more preferably a half-life at pH 2 of less than 60 minutes.
• pro-fragrance silicone polymer When the pro-fragrance silicone polymer is used in granular detergents, the more reactive pro-fragrance silicone polymer, that is, those with half-life at pH 2 of less than one minute, are most suitable, although those having a half-life of less than 60 minutes at pH 0 are also useful.
• pro-fragrance silicone polymers having a half-life of less than 60 minutes at pH 0, and half-life greater than one minute at pH 2 should preferably be used.
• Hydrolysis half-life is determined by UV/V spectroscopy in a 90/10 dioxane/water system at 30°C by following the appearance of the carbonyl absorbance. Because of the hydrophobicity of the pro-fragrance silicone polymer herein, a high dioxane/water ratio is needed to ensure solubility of the pro- fragrance silicone polymer.
• the pH of the water used is achieved by using aqueous HCI.
• the concentration of the pro-fragrance silicone polymer in the dioxane/water system can be adjusted to achieve convenient, measurable absorbance changes.
• Pro-fragrance silicone polymer is weighed out in a 10ml volumetric flask using an analytical balance (Mettler AE 200) Precision is 1/10 mg. The weighed material is dissolved in about 8ml dioxane. Both the dioxane solution of pro- fragrance silicone polymer and aqueous acid solution prepared as described supra are pre-heated in their separate containers to a temperature of 30 + 0.25°C by means of a water-bath. 1 .000ml of aqueous acid solution is added to the pro-fragrance solution by means of an Eppendorf pipetter. This is followed by diluting to the 10ml mark with dioxane. Hydrolysis time is measured, starting upon addition of the acid.
• the pro-fragrance solution is mixed for 30 seconds by shaking, and the solution is transferred to a quartz cuvette.
• the absorbance of the pro-fragrance solution (At) is followed at a regular series of time intervals, and the cuvette is kept in the water-bath at the above-indicated temperature between measurements.
• Initial absorbance (Ao) measurements are carried out using an equal concentration of pro-fragrance in a 90/10 v/v dioxane - deionized water solution, and final absorbance (Af) measurements are taken using the hydrolyzed pro-fragrance solution after the hydrolysis is complete.
• the wavelength at which the hydrolysis is followed is chosen at the wavelength of the absorbance maximum of the starting fragrance carbonyl compound such as aldehydes or ketones.
• Reaction half-lifes are determined using conventional procedures.
• the observed first-order rate constant (k 0D s) is determined by slope of the line provided by plotting the following function vs time (min): Ln [(Ao - Af)/ (A t - Af)] wherein the function is the natural log of the ratio between the absorbance difference at initial time (Ao) and final time (Af) over the absorbance difference at time t (At) and final time (Af).
• Half-life as defined herein is the time required for half of the pro-fragrance silicone polymer to be hydrolyzed, and is determined from the observed rate constant (k 0DS ) by the following function:
• the pro-fragrance silicone polymer of the present invention can be used in a variety of the products in different industries.
• a composition has an effective amount of the pro-fragrance silicone polymer and an acceptable carrier.
• acceptable carrier means one or more compatible solid or liquid filler diluent or encapsulating substances which do not substantially reduce the efficacy of the polymer.
• the specific carrier will depend upon the final form of the composition.
• the acceptable carrier would preferably be carriers which are acceptable during washing and drying, e.g., detersive surfactants, builders, soil releasing agents, and the like.
• the pro-fragrance silicone polymer can be used in a detergent composition.
• the pro-fragrance silicone polymer formulated in a detergent composition is at levels of from about 0.0001% to about 20%; more preferably from about 0.01 % to 10%.
• the pro-fragrance silicone polymer can be used as the sole fragrance compound of the detergent composition, or in combination with other pro- fragrances and/or in combination with other fragrance materials, extenders, fixatives, diluents and the like.
• incorporation of the pro-fragrance silicone polymer into a waxy substance, such as a fatty triglyceride may further improve storage stability of the present pro-fragrance silicone polymer in granular laundry detergents, especially those comprising bleaches.
• hydrophobic liquid extenders, diluents or fixatives can be used to form an emulsion wherein the pro-fragrance silicone polymer is further stabilized by separating it from the aqueous phase.
• Nonlimiting examples of such stabilizing materials include dipropylene glycol, diethyl phthalate and acetyl triethyl citrate.
• hydrophobic perfumery ingredients which can be used to stabilize the pro- fragrance silicone polymer
• detergency ingredients which also have a perfume stabilizing effect and can be formulated with the pro-fragrance silicone polymer.
• Such ingredients include fatty acid amines, low foaming waxy nonionic materials commonly used in automatic dishwashing detergents, and the like.
• pro-fragrance silicone polymers are used along with other fragrance materials in detergent compositions herein, it is preferred that the pro- fragrance silicone polymer be added separately from the other fragrance materials.
• the detergent composition incorporating a detersive surfactant preferably a synthetic detergent surfactants, have a detergent level of from about 0.5% to about 50%, by weight.
• the detergent compositions containing soap preferably include from about 10% to about 90% soap.
• detergent surfactants which are conventional for detergent surfactants can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. See also U.S. Patent 3,664,961 , issued May 23, 1972.
• detergent compositions may further include one or more additional detergent ingredients, commonly used in detergent products, such as materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., conventional perfumes, colorants, dyes, etc.). Such additional ingredients are known to those skilled in the art. The following are illustrative examples of other detergent ingredients.
• Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness and in the removal of particulate soils. Suitable builders include those of U.S. Patent 3,308,067, issued Mar. 7, 1967; 4,144,226, issued Mar. 13, 1979 and 4,246,495, issued Mar. 27, 1979. Inorganic as well as organic builders can be used.
• the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
• the compositions will typically comprise at least about 1 % builder.
• liquid formulations typically comprise from about 5% to about 50%
• granular formulations typically comprise from about 10% to about 80%.
• Soil Release Agents are desirably used in laundry detergents of the instant invention. Suitable soil release agents include those of U.S. Patent 4,968,451 , issued Nov. 6, 1990; the nonionic end-capped 21
• compositions herein can contain other ingredients such as enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known within the art.
• compositions in accordance with the present invention may further, optionally, contain other known compounds having the capability to substantively enhance a fragrance.
• Such compounds include, but are not limited to, the aluminum alkoxides such as isobutylaluminium diferanylate as disclosed in U.S. Patent 4,055,634, issued Oct.
• the pro-fragrance silicone polymer of the present invention may be prepared by the following examples.
• the following examples further describe and demonstrate embodiments within the scope of the present invention.
• the examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
• Example 1
• This example describes the preparation of pro-fragrance silicone polymer of structure V-a.
• This example describes a the preparation of pro-fragrance silicone polymer having structure V-b.
• This example describes the preparation of a pro-fragrance silicone polymer having structure V-c.
• a 50 ml portion of benzene, 20 mmol of 2,4-dimethyl-3-cychexyl carboxyaldehyde, 10 mmol of aminopropyl polysiloxane, and 0.016 mol of p- toluenesulfonic acid are stirred in a round-bottomed flask with Dean-Stark attachment under reflex for 24 hours.
• the reaction mixture is washed several times with aqueous Na2CO3 solution and is extracted as an organic solution.
• the organic solution is then dried over Na2CO3 and Na2SO4.
• the organic solution is evaporated in vacuo after filtration. A 99.2% yield of the compound (V-c and c') is obtained.
• This example describes a granular laundry composition having the pro- fragrance silicone polymer of Example 1 ,
• Enzyme (SavinaseTMand/or LipolaseTMfrom Novo) 1.4
• the pro-fragrance silicone polymer obtained has at least one schiff base moiety, thereby the compound can provide a fabric softening effect and desirable odor including release of fragrance by hydrolysis of the compound.

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• 1998
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