AU6554298A

AU6554298A - Pro-fragrance silicone polymer and compositions thereof

Info

Publication number: AU6554298A
Application number: AU65542/98A
Authority: AU
Inventors: Masahiro Ishida; Masami Ono
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1998-03-12
Filing date: 1998-03-12
Publication date: 1999-09-27
Also published as: WO1999046318A1; CN1292807A; TR200003601T2; JP2000510527A; BR9815725A; CA2323488A1; EP1062265A1

Description

WO 99/46318 PCT/US98/04950 1 PRO-FRAGRANCE SILICONE POLYMER AND COMPOSITIONS THEREOF 5 TECHNICAL FIELD The present invention relates to a pro-fragrance silicone polymer and compositions thereof, more specifically a pro-fragrance silicone polymer derived o10 from an aminoalkyl polysiloxane and a fragrance carbonyl compound. BACKGROUND Most consumers have come to expect pleasingly scented laundry products, as well as such products imparting the pleasing scent to laundered 15 fabrics. Consumers also desire that laundered fabrics retain a pleasant fragrance over time. Perfume additives have been employed to impart an aesthetically pleasing scent to laundry products such as laundry detergents and fabric conditioners. In some case, these perfumes also impart their fragrance to fabrics treated with the perfumed laundry product. Consumers have also come 20 to expect laundry products which provide a soft and/or smooth tactile sensation to the laundered products. Additionally, consumers have come to expect hair products which produce a pleasing scent and providing softness to the hair. Certain odoriferous acetals and ketals capable of producing additional desirable odor upon hydrolysis, have long been known in perfumery. See 25 Steffen Arctander, "Perfume and Flavor Chemicals," Arctander, N.J., 1969, and U.S. patent 5,378,468, Suffis et al., issued January 3, 1995. Certain classes of acetals and ketals, formulated into detergent compositions can produce a delayed release of fragrance. Such pro-fragrance acetals and ketals, once deposited onto fabrics during washing process, tend to produce pleasing 30 fragrances upon hydrolysis of the acetals and ketals by humidity and sweat during wearing of the laundered fabrics. See, PTC/US96/04060, Mao et al. 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. Depending on structures and properties of silicone polymers, there are two 35 main areas for the use of such silicone polymer. One area is for surface treating WO 99/46318 PCT/US98/04950 2 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 5 materials such as fabrics and hair. In addition, 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, 10 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, 15 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 20 the hair, these silicone polymers are formulated into applications such as detergents and softeners for daily washing in addition to pre-treatment. However, neither of these approaches successfully provide a pro fragrance silicone polymer having improved deposition onto fabric and/or hair, providing softness, and/or releasing a pleasant fragrance by hydrolysis. 25 Based on the foregoing, there is a need for providing a pro-fragrance silicone polymer that can provide a fabric and/or hair softening effect, and/or desirable post-deposition release of a pleasant odor. SUMMARY 30 A pro-fragrance silicone polymer comprising the following structure: R1 R3 R5 R6 I I I l1 X-Si-O -- iSi-O---HSi-O Si-Y I I R2 R4 Z R7

(I).

WO 99/46318 PCT/US98/04950 3 X, Y, and Z are independently the following: (CH2)a-Q c(CH 2 )b-N

=

C-W I i. V (II); V I r (C H2)e-N= C- W (CH2)d--N CH - -W ii. V (III); P (CH2)h-N=C-W I I. V (IV); or 5 iv. a hydrocarbons of 1 to about 10 carbons or 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, wherein the first randomly repeating monomer unit is -(CH2)j-NH lo and the second randomly repeating monomer unit is (CH2)k-N 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 independently hydrocarbons of 15 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 20 about 20; j is an integer of 1 to about 20; and k is an integer of 1 to about 20. These and other features, aspects, and advantages of the present invention will become better understood from a reading of the following description, and appended claims.

WO 99/46318 PCT/US98/04950 4 DETAILED DESCRIPTION While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description. 5 All percentages and ratios used hereinafter are by weight of total composition, unless otherwise indicated. All measurements referred to herein are made at 250C unless otherwise specified. All percentages, ratios, and levels of ingredients referred to herein are 10 based on the actual amount of the ingredient, and do not include solvents, fillers, or other materials with which the ingredient may be combined as a commercially available product, unless otherwise indicated. All publications, patent applications, and issued patents mentioned herein are hereby incorporated in their entirety by reference. Citation of any reference 15 is not an admission regarding any determination as to its availability as prior art to the claimed invention. Herein, "comprising" means that other steps and other components which do not affect the end result can be added. This term encompasses the terms "consisting of" and "consisting essentially of." 20 Herein, "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. Herein, "schiff base" refers to a class of unit obtained by chemical reaction (e.g., condensation, dehydration) from an aldehyde or a ketone with primary 25 amines. The general formula is R(R')C=NR". Herein, "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." Herein, "aminoalkyl polysiloxane," is a polymer which contains -Si(R) 2

-O

30 repeating units and at least one aminoalkyl substituent of

-R-NH

2 in terminal or branched position. Herein, "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.

WO 99/46318 PCT/US98/04950 5 Herein, "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. 5 Herein, "alkyl" means a carbon-containing chain, which may be straight, branched, or cyclic; saturated or unsaturated; and substituted (mono- or poly-) or unsubstituted. Herein, "alkoxyl" means -O-R, wherein R is alkyl, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy. o10 A. Pro-fragrance Silicone Polymer The present invention relates to a pro-fragrance silicone polymer comprising the following structure: R1 R3 R 5 R6 I I 1 1 X-Si-O Si-O----Si-O -- i-Y I I m I n I R2 R4 Z R7 ). X, Y, and Z are independently the following: -(CH2)a-Q (CH 2 )b-N=C-W I i. V (II); 15 V I

H(CH

2 )e-N=C-W -(C H2)d--Nig (C H2)f-N=C-W I ii. V (III); P -(CH2)h-N=C-W I iii. 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 20 a second randomly repeating monomer unit (hereinafter "RRMU"), wherein the first RRMU is

-(CH

2 )j-NH and the second RRMU is WO 99/46318 PCT/US98/04950 6 (CH2)k-N 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 5 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 10 integer of 1 to about 20; and k is an integer of 1 to about 20. In the above structure, X, Y, and Z are the same or different from one another selected from the group consisting of the following formula: -(CH2)a-Qc (CH 2 )b-N=C-W cI i. V (II); V I _(CH2)e-N--C-W (C H 2 )d--Ng (CH2)f-N-C-W ii. V (III) P (CH 2 )h-N=C-W I III. V 15 (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

(CH

2 )j-NH 20 and the second RRMU is

(CH

2 )k-Nj Preferably, a is an integer of 1 to about 6; b is an integer of 1 to about 10; c is an integer of 0 to about 10; d is an integer of 1 to about 6; e is an integer of 1 to about 10; f is an integer of 1 to about 10; g is an integer of 1 to about 20; h is WO 99/46318 PCT/US98/04950 7 an integer of 1 to about 10; j is an integer of 1 to about 6; and k is an integer of 1 to about 6. Preferably, 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, 5 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are methyl or phenyl. In the above structure, X and Y are the same or different and are formula (II), (III), (IV), or hydrocarbons of 1 to about 10 carbons or phenyl. Preferably, when X and Y are the same, X and Y are formula (II) or a hydrocarbon of 1 to about 10 carbons or a phenyl. When X and Y are different, at least one of X and 10 Y are preferably formula (II), (III), or (IV). When one of X and Y are 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. In the above structure, preferably, Z is formula (II), (III), or (IV) when X and Y are hydrocarbons of 1 to about 10 carbons or phenyl; more preferably X 15 and Y are the same. In another embodiment, Z can be formula (II), when X and Y are the same, preferably formula (II). There are any combinations of formula (II), (III), and (IV) for X, Y and Z, depending on size and structure of formula (e.g., configuration, and numbers of repeating unit such as -(CH 2 )- of formula (II) and (III) or the first and second 20 RRMU of formula (IV).) Such size and balk of structure generally cause steric effects to the structure (I), thereby formula (II), (III), and (IV) leading to suitable positions of X, Y, and Z. The formula (II), (III), and (IV) herein include a schiff base unit having a general formula -N=C(V)W which originates in fragrance carbonyl compounds 25 such as aldehydes or ketones. 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. When V and 30 W are derived from aldehydes, 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. When V and W are derived from ketones, both V and W are preferably hydrocarbons of 1 to about 30 carbons.

WO 99/46318 PCT/US98/04950 8 In one embodiment, V and W can be bonded together to form a ring. When V and W form a ring, the fragrance carbonyl compound is a cyclic carbonyl compound. Preferably, the sum of V and W contains 1 to about 50 carbons. In another embodiment, the pro-fragrance silicone polymer can include 5 two of formula (II) substituents. In this embodiment, 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)): R1 R 3

R

5

R

6 I I I W-C=N-(CH2)b Q-(CH2)aSi-O Si-OHi-O i-S-I (CH2)a-Q -(CH2)b-N=C-W IV N(H)iQ(H) ImI n I V V R 2

R

4 Z R 7 V wherein V and W are hydrogen or straight, branched, or cyclic, saturated or 10 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; H CH 3

CH

3 H H H

-N(CH

2

)

3 -Si-O Si-(CH 2

)

3 N 1 9 1V-a

CH

3

CH

3 15 which is derived from 2-methyl-3-(4-t-butylphenyl)-propanal (lily aldehyde) and aminopropyl polysiloxane, H CH 3 CH3 H N(CHi2)3-1i-O - i-(CH2)3N V-b 1 9 1 CH3 CH3 which is derived from 2-hexyl-3-phenyl-2-propenal (a-hexyl cinnamic aldehyde) and aminopropyl polysiloxane, and WO 99/46318 PCT/US98/04950 9

CH

3

CH

3 H I IH

HN(CH

3

)

3 -f Si-O-- Si-(CH 3

)

3 N (V-c), and H 1 91

CH

3

CH

3 H

CH

3

CH

3 I I

N(CH

3

)

3 -Si-O+ -Si-(CH 3

)

3 N (V-c') I I H

CH

3

CH

3 which are derived from 2,4-dimethyl-3-cyclohexyl carboxyaldehyde and aminopropyl polysiloxane. 5 Another preferred embodiment of the pro-fragrance silicone polymer having formula (II) at position Z of structure (I) is the following (structure VI):

R

1

R

3

R

5

R

6 I I 1 r X- S i- O i-O Si-O I (VI) R2 R4 I R7 [(CH2)a-Q-- (CH 2 )b-N=C-W C V wherein 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 10 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. Specific preferred pro-fragrance silicone polymers having the structure (VI) are nonlimitingly illustrated by the following:

CH

3

CH

3

CH

3

CH

3 I I I I(VI-a) H3C-Si-O--Si-O Si-O- Si-CH 3 (VI-a) I I n f i

CH

3

OH

3 CH 3 H

C

3

H

6

NHC

2

H

4 N 15 wherein m is integer from about 26 to about 30; n is integer from 2 to about 6.

WO 99/46318 PCT/US98/04950 10 When the above structure (VI) include formula (IV) instead of formula (II), the pro-fragrance silicone polymer is a highly branched compound having the following structure: R1 R 3 R5 R6 I , I , I V X-Si-O Si-O---Si-0 -Si-Y V I t- I ,m I n I V I R52 k 4 R7 I

W-C-N-(CH

2 )h R 2

R

4 7 (CH 2 )h-N=C-W W NCH N-(CH2)k CH2)k-N (CH2)k (CH2)h-N=C-W W-C=N-(CH2)h I I V /v v V N-(CH 2 )k-N-(CH 2 )k VI V I (CH2)-N

(C

H

2 )h-N

=

C-W S1/(CH2)k-N (CH2)h-N=C-W (VI-b) W-CU= N-(CH 2 )h N W-C=N-(CH 2 )h / V I I V (CH2)kN- -(CH2)h-N=C-W

(CH

2 )h-N=C-W I V 5 Other preferred pro-fragrance silicone polymers useful herein is the following (structure VII):

R

1

R

3

R

5

R

6 W-c-N-(CH2)bt Q- (CH2)a i-O - i-0~ i-O i (CH 2 )a-Q (CH2)b-N=C-W 02 R 4 m n7 c (VII) (CH2)a-Qc (CH2)b-N=Cw-W CI V wherein 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 10 500; and n is an integer of 1 to about 100. In another preferred embodiment, the pro-fragrance silicone polymer of the present invention includes the following (structure VIII):

R

1

R

3

R

5

R

6 I I I X-Si-O Si-O S i-O - S i(CH2)a-Q -(CH 2 )b-N=C-W m n C (VM)

R

2

R

4 Z R7 V WO 99/46318 PCT/US98/04950 11 wherein 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 5 an aminoalkyl polysiloxane and a fragrance carbonyl compound by condensation which produces a schiff base unit. Such fragrance sources of the pro-fragrance silicone polymer produce a pleasant fragrance. Without being bound by theory, it is believed that due to less volatility, a silicone polymer (e.g., aminoalkyl polysiloxane) generally produces little smell so that the pro-fragrance silicone 10 polymer derived herein in itself tends to be smelled weakly during depositing onto the surface, e.g., of fabric or hair. 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. 15 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 20 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 25 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 30 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 35 humidity. Such a reduction in pH is preferably at least about 0.1, more preferably WO 99/46318 PCT/US98/04950 12 at least about 0.5 units. Preferably 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. Preferably, 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 5 designed to readily disperse in aqueous solution and thereby result in reasonably good deposition, e.g., from laundering solution onto fabric. B. Aminoalkyl Polysiloxane The pro-fragrance silicone polymer of the present invention can be derived from an aminoalkyl polysiloxane and a fragrance carbonyl compound by 10 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. For 15 example, 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 20 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. (US); tradename X-22-161AS, X-22-161A, X-22-161B, KF-8012, KF-393, KF-859, KF-860, KF-861, KF-867, KF-869, KF-880, KF-8002, KF-8004, KF-8005, KF-858, KF-864, KF-865, KF-868, and KF-8003, supplied by 25 ShinEtsu Chemical Industrial Co. Ltd.; tradename TSF4700, TSF4701, TSF4702, TSF4703, TSF4704, TSF4705, TEX150, TEX151, TEX154, TSF4706, TSL9346, TSL9386, TSL9306, SF1921, SF1925, SF1708-D1, SM2658, SF1708, SF1921, SF1925 and SM2658, supplied by Toshiba Silicones, KK; tradename SM8702, SM8702C, SM8709, SF8411, SF8417, BY16-828, BY16-849, BY16 30 850, BY16-853, BY16-853B, BY16-872, BY22-007, BY22-812, BY22-816, BY22 819, and BY22-823, supplied by Toray Dow Corning Silicone, KK. C. Fragrance Carbonyl Compound Fragrance carbonyl compounds useful herein derives the pro-fragrance silicone polymer of the present invention.

WO 99/46318 PCT/US98/04950 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 5 such as alcohols, esters, or ethers as well. Preferably, 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, 10 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), tridecyl aldehyde, 3,5,5-trimethylhexanal, 2 15 methyldecanal (methyloctylacetaldehyde), 2-methylundecanal (methylnonylacetaldehyde), trans-2-hexenal (leaf aldehyde), cis-4-heptenal, trans-2-cis-6-nonadienal (cucumber aldehyde), cis-4-decenal, trans-4-decenal, 10-undecen-1l-al (undecenoic aldehyde), trans-2-dodecenal, 2,6,10-trimethyl-9 undecenal, 2,6,10-trimethyl-5,9-undecadienal, 3,7-dimethyl-2,6-octadienal 20 (citral), 3,7-dimethyl-6-octen-l1-al (citronellal), 7-hydroxy-3,7-dimethyloctan-l1-al (hydroxy citronellal), p-mentha-1,8-dien-7-al (perilla aldehyde). Examples of the terpenic aldehyde useful for the pro-fragrance silicone polymer herein include 3 ,7-dimethyl-7-methoxyoctan-1 -al (methoxydihydrocitronellal), citronellyloxy acetaldehyde, 2,4-diemthyl-3 25 cyclohexenyl carboxyaldehyde, 2,4,6-trimethyl-3-cyclohexene- 1 carboxyaldehyde (isocyclocitral), 5-methoxy-octahydro-4,7-menthano-l1H-indene 2-carboxyaldehyde (scentenal), 4

-(

4 -methyl-3-pentenyl)-3-cyclohexen-1 carboxyaldehyde (myrac aldehyde), 4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexen 1-carboxyaldehyde (lyral), 1-methyl-4-(4-methyl-pentyl)-3-cyclohexen 30 carboxyaldehyde (vernaldehyde), 4-(tricyclo[5.2.1.02 ,6 ]decyliden-8)-butenal (dupical), 7-formyl-5-isopropyl-2-methyl-bicyclo-[2.2.2]oct-2-ene (maceal), 2 methyl-4-(2,6,6-trimethyl-1 -cyclohexen-1 -yl)-2-butenal (boronal), 2-methyl-4 (2,6,6-trimethyl-2-cyclohexen-1-yl)-butanal (cetonal). Examples of the aromatic aldehyde useful for the pro-fragrance silicone 35 polymer of the present invention include benzaldehyde, phenylacetaldehyde WO 99/46318 PCT/US98/04950 14 (hyacinth aldehyde), 3-phenylpropanal (phenylpropylaldehyde), 3-pheny-2 propenal (cinnamic aldehyde), 2-pentyl-3-phenyl-2-propenal (c-amyl cinnamic aldehyde), 2-hexyl-3-phenyl-2-propenal (a-hexyl cinnamic aldehyde), 2 phenylpropanal (hydratropic aldehyde), 4-methoxybenzaldehyde (anis aldehyde), 5 p-methylphenylacetaldehyde (p-tolyl acetaldehyde), 4-isopropylbenzaldehyde (cumin aldehyde), 2 -methyl-3-(4-isopropylphenyl)-propanal (cyclamen aldehyde), 3-(p-t-butylphenyl)-propanal, 3-(p-ethylphenyl)-2,2-dimethylpropanal (p-ethyl 2,2 dimethylhydrocinnamic aldehyde), 2 -methyl-3-(p-methoxyphenyl)-propanal, 2 methyl-3-(4-t-butylphenyl)-propanal (4-t-butyl-a-methylhydrocinnamic aldehyde, 10 lily aldehyde), 2-hydroxybenzaldehyde (salicylic aldehyde), 3,4-methylenedioxy benzaldehyde (heliotropine), 2 -methyl- 3 -(3,4-methylenedioxy-phenyl)-propanal (helional), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3-ethoxy-4 hydroxybenzaldehyde (ethyl vanillin), 3,4-dimethyoxy-benzaldehyde (methyl vanillin): aldehydes having low volatility by virtue of incorporation of bulky polar 15 moieties. 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 20 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 25 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 (d-pulegone), p-menth-1l-en-3-one (piperitone), 1,3,3-trimethyl-bicyclo[2.2.1]heptan-2-one 30 (fenchone), 6 ,10,-dimethyl-5,9-undecadiene-2-one (geranyl acetone), acetyl cedrene (cedryl methyl ketone), 5,6-dimethyl-8-isopropenylbicyclo-[4.4.0]-l decen-3-one (nootkatone), 4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (ca -ionone), 4-(2,2,6-trimethyl-1l-cyclohexen-1-yl)-3-buten-2-one (P-ionone), 5 (2,2,6-trimethyl-2-cyclohexen-1-yl)-4-pentan-3-one (Cu-methyl ionone), 5-(2,2,6 35 trimethyl-1l-cyclohexen-1-yl)-4-pentan-3-one (1-methyl ionone), 5-(2,2,6-trimethyl- WO 99/46318 PCT/US98/04950 15 2-cyclohexen-1-yl)-3-methyl-3-buten-2-one (y-methyl ionone), 5-(2,2,6-trimethyl 1-cyclohexen-1-yl)-3-methyl-3-buten-2-one (8-methyl ionone), 1-(2,2,6-trimethyl 2-cyclohexen-1-yl)-1,6-heptadien-3-one (allyl ionone), Co-irone, P3-irone, y-irone, 1 (2,2,6-trimethyl-2-cyclohexen-1 -yl)-2-buten-1 -one (ca-damascone), 1-(2,2,6 5 trimethyl-1 -cyclohexen-1 -yl)-2-buten-1 -one (P-damascone), 1-(2,2,6-trimethyl-3 cyclohexen-1 -yl)-2-buten-1-one (8-damascone), 1-(3,3-dimethyl-6-cyclohexen-1 yl)-penta-4-en-1-one (cu-dynascone), 1-(3,3-dimethyl-l1-cyclohexen-1-yl)-penta-4 en-1-one (1-dynascone). Examples of the cyclic ketone include 3-hydroxy-2-methyl-4H-pyran-4-one 10 (maltol), 2-ethyl-3-hydroxy-4H-pyran-4-one (ethyl maltol), 2,5-diemthyl-4-hydroxy 2H-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-l1-one (cis-jasmone), 6 (or 7)-ethylidene-octahydro-5,8-methano-2H 15 benzopyrane (florex), 7-methyl-octahydro-1,4-methanonaphthalen-6(2H)-one (plicatone), 4-cyclohexyl-4-methyl-2-pentanone, 1 -(p-menthen-6(2)-yl)- 1 propanone, 2 ,2,5-trimethyl-5-pentylcyclopentanone, 4-(1-ethoxyvinyl)-3,3,5,5 tetramethyl-cyclohexanone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 7-acetyl-1,2,3,4,5,6,7,8-octahydro- 1, 1,6,7-tetramethylnaphthalene (Iso E Super), 20 methyl 2,6,10-trimethyl-2,5,9,cyclododecatrien-1-yl ketone (trimofix "O"). Examples of the aromatic ketone includes, 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 25 hydroxy-3-methoxyphenyl)-2-butanone (Zingerone), 2-acetonaphthone (methyl P3 naphthyl ketone), 4-phenyl-4-methyl-2-pentanone, and benzophenone (diphenyl ketone). Other exemplary ketones include Ethyl ketopropinate (ethyl pyruvate), isoamyl ketopropionate (isoamyl pyruvate), ethyl acetoacetate, ethyl y ketovalerate (ethyl levulinate), methyl jasmonate, and methyl dihydrojasmonate. 30 D. Method of Making Pro-fragrance Silicone Polymer 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. For making the pro- WO 99/46318 PCT/US98/04950 16 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 5 sulfonic acid, methane sulfonic acid, sulfuric acid, hydrochloric acid, sulfosalicylic acid, and mixtures thereof or supported sulfonic acid catalysts, e.g., AMBERLYST 15TM. When the catalysis is sensitive to strong acid conditions and can undergo undesirable side reactions, acid catalysts with pKa's among 3 and 4 are the most desirable to minimize unnecessary side-reaction. Non-acidic lo 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 15 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 Acta (1) 10 (1983), Bunton, C.A. et al, J. Org. Chem. (44), 3238, (1978), and Cort, O., et 20 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 25 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 pressurization causes the fragrance carbonyl compound and the aminoalkyl polysiloxane to react and form the pro-fragrance silicone polymer. Herein, "pressurizing" means changing any condition of the reaction for deriving the pro 30 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 pressurization herein is achieved by heating. Preferably, step (a) 35 further comprises adding a catalyst, solvent, a dehydrating agent, or mixtures WO 99/46318 PCT/US98/04950 17 thereof. 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, sulfuric acid, hydrochloric acid, and sulfosalicylic acid preferably) and non-acidic catalysts (e.g., Girder KSF, boron trifluoride etherate, potassium 5 hydrogen sulfate, copper sulfate, and ion excharger), preferably a Lewis acid. E. Test Methods for Determining Hydrolysis Half-life (t-1/2) 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 o10 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. 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 15 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. For liquid detergent applications, 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 20 dioxane/water system at 300C 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 25 dioxane/water system can be adjusted to achieve convenient, measurable absorbance changes. All measurements are carried out using a Hewlett Packard 8452 A Diode Array Spectrophotometer using quartz 1 cm path length cuvette cells. Materials used include 1,4-dioxane HPLC Grade 99.9% (Sigma-Aldrich), 1N HCI volumetric 30 solution (J.T. Baker), deionized water filtered with MilliQPlus (Millipore) at resistivity of 18.2 M Ohm cm. The pH's are measured using an Orion 230 A standardized with pH 4 and pH 7 buffers. The 1N HCI standard is used directly for pH 0 conditions. For pH 2 conditions, 1N HCI is diluted with deionized water. Pro-fragrance silicone polymer is weighed out in a 10ml volumetric flask 35 using an analytical balance (Mettler AE 200) Precision is 1/10 mg. The weighed WO 99/46318 PCT/US98/04950 18 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 + 0.250C by means of a water-bath. 1.000ml of aqueous acid solution is added to 5 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, 10 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 15 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 (kobs) is determined by slope of the line 20 provided by plotting the following function vs time (min): Ln [(Ao - Af)/ (At - 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). 25 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 (kobs) by the following function: Ln (1/2) = -kobs t 1/2 F. Method of Use 30 1. Acceptable Carrier The pro-fragrance silicone polymer of the present invention can be used in a variety of the products in different industries. For example, the products which desire the release of fragrances and providing softness to the hair and fabrics. In another aspect of the present invention, a composition has an effective 35 amount of the pro-fragrance silicone polymer and an acceptable carrier. Herein, WO 99/46318 PCT/US98/04950 19 "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. For example, when the composition is a laundry detergent composition, the 5 acceptable carrier would preferably be carriers which are acceptable during washing and drying, e.g., detersive surfactants, builders, soil releasing agents, and the like. 2. Detergent Composition The pro-fragrance silicone polymer can be used in a detergent 10 composition. Preferably, 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 15 fragrances and/or in combination with other fragrance materials, extenders, fixatives, diluents and the like. For example, 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. In liquid or gel forms 20 of detergent compositions, 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. Just as there exist 25 hydrophobic perfumery ingredients which can be used to stabilize the pro fragrance silicone polymer, there also exist 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 30 like. In general, where 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.

WO 99/46318 PCT/US98/04950 20 a. Detersive Surfactants 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 5 include from about 10% to about 90% soap. Many 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. 10 The detergent compositions herein, preferably, have a pH of from about 7.1 to about 13, more typically from about 7.5 to about 9.5 for liquid detergents and from about 8 to about 12 for granular detergents when measured at 1% concentration of the distilled water at 200C. b. Additional Detergent Ingredients 15 In addition to the pro-fragrance silicone polymer, 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, 20 dyes, etc.). Such additional ingredients are known to those skilled in the art. The following are illustrative examples of other detergent ingredients. (i) 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, 25 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. When present, the compositions will typically comprise at least about 1% builder. Preferably, liquid formulations 30 typically comprise from about 5% to about 50%, and granular formulations typically comprise from about 10% to about 80%. Lower or higher levels of builder, however, are not meant to be excluded. (ii) Soil Release Agents - Soil Release agents are desirably used in laundry detergents of the instant invention. Suitable soil release agents include 35 those of U.S. Patent 4,968,451, issued Nov. 6, 1990; the nonionic end-capped WO 99/46318 PCT/US98/04950 21 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. Patent 4,711,730, Dec. 8, 1987; the partly- and fully- anionic-end-capped oligomeric esters of U.S. Patent 4,721,580, issued Jan. 26, 1988; the nonionic-capped block polyester oligomeric compounds of U.S. Patent 4,702,857, issued Oct. 27, 1987; 5 and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Patent 4,877,896, issued Oct. 31, 1989. Another preferred soil release agent is a sulfonated end-capped type described in U.S. Patent 5,415,807. c. Other Inqredients The compositions herein can contain other ingredients such as enzymes, 10 bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known within the art. d. Formulations With or Without Conventional Perfumery Materials While the pro-fragrance silicone polymer of the present invention can be used alone and simply mixed with essential detergent ingredient, most notably 15 surfactant, they can also be desirably combined into three-part formulations which combine (a) a non-fragrance detergent base containing one or more synthetic detergents, (b) one or more pro-fragrance silicone polymers in accordance with the invention and (c) a fully-formulated fragrance. The latter provides desirable in-package and in-use (wash-time) fragrance, while the pro 20 fragrance provides a long-term fragrance to the laundered textile fabrics. It is preferred that the pro-fragrance silicone polymer be added separately from the conventional fragrances to the detergent compositions. e. Formulations with other Special-Purpose Fraqrance Delivering Compounds 25 Detergent 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. 25, 1977; or the known titanate and 30 zirconate esters or oligoesters of fragrant materials such as those disclosed in U.S. Patent 3,947,574, issued March 30, 1976 and U.S. Patent 3,779,932, issued Dec. 18, 1973. When using such organoaluminium, organotitanium or organozinc derivatives, they may be incorporated into the detergent compositions of the present invention described herein at their art-known levels.

WO 99/46318 PCT/US98/04950 22 EXAMPLES 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 5 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 10 of structure V-a. A 50 ml portion of benzene, 40 mmol of 2-methyl-3-(4-t-butylphenyl) propanal (lily aldehyde), 20 mmol of aminopropyl polysiloxane, and 0.031 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 15 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 95.3% yield of the compound (V-a) is obtained. An embodiment of this example is shown in the following scheme: 0

CH

3

CH

3 H I I H 2

N(CH

2

)

3 Si-O Si-(CH 2

)

3

NH

2 1 9 1 20

CH

3

CH

3 p-TsOH in benzen H CH3 OH 3 H I I

N(CH

2

)

3 + Si-O- -Si-(CH 2

)

3 N

CH

3

CH

3 (V-a) Example 2 This example describes a the preparation of pro-fragrance silicone polymer having structure V-b. 25 A 50 ml portion of benzene, 20 mmol of 2-hexyl-3-phenyl-2-propenal (a hexyl cinnamic aldehyde), 10 mmol of aminopropyl polysiloxane, and 0.016 mol WO 99/46318 PCT/US98/04950 23 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 5 solution is evaporated in vacuo after filtration. A 97.5% yield of the compound (V-b) is obtained. Example 3 This example describes the preparation of a pro-fragrance silicone polymer having structure V-c. 10 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. 15 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.

WO 99/46318 PCT/US98/04950 24 Example 4 This example describes a granular laundry composition having the pro fragrance silicone polymer of Example 1, component % weight .Pro-fragrance Silicone Polymer of Example 1 ...... 1.0. C11-C13 Dodecyl Benzene Sulfonate ....... 21.0. C12-C13 Alkyl Ethoxylate EO 1-8 1.2 Sodium Tripolyphosphate 34.0 Zeolite Na 4A 14.0

.................................-----------------------------------------------

Sodium Silicate 2.0 ratio 2.0 ------------------------------------------------------

--------

Sodium Carbonate 23.4 -Sdim aroat----------------------------------------- --- 2--- Enzyme (SavinaseTMand/or Lipolasemfrom Novo) 1.4 ------------------------------------------------------

--------

Carboxymethyl Cellulose 0.3 ------------------------------------------------------

--------

Anionic Soil Release Agent *1 0.3 ------------------------------------------------------ -------- ..Bri-ghtener ....................................................... 0.2 Silicone Suds Suppressor (Dow Corning Corp) 0.2 Perfume *2 0.3 ------------------------------------------------------ -------- Sodium Sulfate 0.5 Moisture balance up to 100 5 *1 See U.S. 4,968,451 *2 Perfume composition of the following formula: component % weight .Benzyl salicylate ----------- --------- 20. Ethylene brassylate -------- --------- - 20 . .Galaxolide (50% soln. in -benzyl_ benzoate) ... 20_ Hexyl cinnamic aldehyde ------------ 20_ Tetrahydro linalool ................ 20 total 100 The embodiments disclosed and represented by the previous examples have many advantages. For example, the pro-fragrance silicone polymer 10 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.

WO 99/46318 PCT/US98/04950 25 It is understood that examples and embodiments described herein are for illustrative purpose only and that various modifications or changes in right thereof will be suggested to one skill the art and are to be included in the spirit and purview of this application and scope of the appended claims. 5

Claims

1. A pro-fragrance silicone polymer comprising the following structure: R1 R3 R 5 R6 I I I I X-Si-O si-O si-O Si-Y I - I m I n I R2 R4 Z R7 wherein 5 a. X, Y, and Z are independently: (CH2)a-Q- (CH 2 )b-N C-W cI i. V (II); V (CH2)d (CH2)e-N=C-W 4(CH2)d-N g (CH2)f-N=C-W I ii. V (III); -P -(CH 2 )h-N=C-W I iii. V (IV); wherein P has a first and a second randomly repeating 10 monomer unit, wherein the first randomly repeating monomer unit is -(CH 2 )j-NH and the second randomly repeating monomer unit is (CH 2 )k-N ; or 15 iv. a hydrocarbon of 1 to about 10 carbons or phenyl; wherein at least one of X, Y, and Z is formula (II), (III), or (IV); b. Q is oxygen, sulfur, or -NH-; c. V and W are independently hydrogen; or straight, branched, or cyclic, saturated or unsaturated hydrocarbons of 1 to about 30 20 carbons; WO 99/46318 PCT/US98/04950 27 d. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently hydrocarbons of 1 to about 10 carbons or a phenyl; e. m is an integer of 0 to about 500; f. n is an integer of 0 to about 100; 25 g. the sum of m and n is an integer of at least 1; h. a is an integer of 1 to about 20; i. b is an integer of 1 to about 20; k. c is an integer of 0 to about 100; I. d is an integer of 1 to about 20; 30 m. e is an integer of 1 to about 20; n. f is an integer of 1 to about 20, o. g is an integer of 1 to about 100; p. h is an integer of 1 to about 20; q. j is an integer of 1 to about 20; and 35 r. k is an integer of 1 to about 20.

2. The pro-fragrance silicone polymer of Claim 1, wherein the pro-fragrance silicone polymer comprises at least one schiff base unit derived from an aminoalkyl polysiloxane and a fragrance carbonyl compound.

3. The pro-fragrance silicone polymer of Claim 2, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently an alkyl of 1 to about 10 carbons or a phenyl.

4. The pro-fragrance silicone polymer of claim 3, wherein V and W can be bonded together to form a ring having branched, saturated or unsaturated, hydrocarbons of 1 to about 50 carbons.

5. The pro-fragrance silicone polymer of Claim 3, wherein X, Y, and Z are independently formula (II), (III), (IV), or an alkyl of 1 to about 10 carbons or a phenyl, wherein at least one of X, Y, and Z are formula (II), (III), or (IV); a is an integer of 1 to about 6; b is an integer of 1 to about 10; c is an integer of 0 to 5 about 10; d is an integer of 1 to about 6; e is an integer of 1 to about 10; f is an integer of 1 to about 10; g is an integer of 1 to about 20; h is an integer of 1 to about 10; J is an integer of 1 to about 6; and k is an integer of 1 to about 6. WO 99/46318 PCT/US98/04950 28

6. The pro-fragrance silicone polymer of Claim 5, wherein X and Y are the same and are formula (II), (III), or (IV); and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and Z are the same and are an alkyl of 1 to about 10 carbons or a phenyl.

7. The pro-fragrance silicone polymer of Claim 5, wherein Z is formula (II), (III), or (IV); and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Y are the same and are an alkyl of 1 to about 10 carbons or a phenyl.

8. The pro-fragrance silicone polymer of Claim 5, wherein X, Y and Z are the same and are formula (II), (III), or (IV).

9. The pro-fragrance silicone polymer of Claim 5, wherein at least one of X and Y are formula (II), (III), or (IV); and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and Z are the same and are an alkyl of 1 to about 10 carbons or a phenyl.

10. A composition comprising the pro-fragrance silicone polymer of Claim 1 and an acceptable carrier.