NZ298935A - Silicone compositions; comprise aminoalkylsilicone - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £98935 New Zealand No International No 298935 PCT/US95/1 5766 TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates 22 12 1994, Complete Specification Filed 05 12 1995 Classification (6) A61K7/46, A23L1/226 Publication date 28 October 1999 Journal No 1445 NO DRAWINGS NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention S'licone compositions Name, address and nationality of applicant(s) as in international application form THE PROCTER & GAMBLE COMPANY, One Procter & Gamble Plaza, Cincinnati, Ohio 45202, United States of America . - Q n H 1 SILICONE COMPOSITIONS TECHNICAL FIELD The present invention relates to silicone-containing compositions and to use thereof m various household products such as personal care products, laundry and household cleaners, bleaching compositions and the like. In particular, it relates to silicone-containing lipophilic compositions based on flavorants, perfumes, coolants or antimicrobial agents as lipophile and which display improved residuality, impact and/or efficacy on surfaces treated therewith, for example teeth, dentures, skin, hair, laundry, dishware, working surfaces and the like. In addition, it relates to silicone-containing bleach compositions which additionally contain bleach-sensitive ingredients such as perfumes, flavorants and the like and which display improved stability.

BACKGROUND Lipophilic compositions such as flavor, perfume, coolant and disinfectant compositions are widely used either directly or m a variety of household products inclusive of cosmetics, oral and denture compositions, bleach, dishvvashing, hard surface cleaning and laundry detergent products, etc A common problem encountered with lipophilic compositions is that of improving surface substantivity or residuality of the lipophilic component It would be desirable m many if not most household applications to enhance the surface residuality of the lipophile m order, for example, to provide increased flavor or perfume impact or increased antimicrobial efficacy.

Modern dental hygiene and denture preparations, for example, typically contain antiplaque and/or antitartar agents, as well as antimicrobial agents and flavorants. Antimicrobial action could affect plaque formation by either reducing the number of bacteria in the mouth/dentures or by killing those bacteria trapped in the film to prevent further growth and metabolism. Flavorants may alleviate the problem of bad breath via a deodorizing action. Some antimicrobial agents, e.g. menthol may, also PC )| U 'S95/15766 2 serve as breath deodorizers. However, the efficacy of antimicrobial agents depends largely on their mtraoral/denture retention, particularly their retention on the surface of the teeth or dentures where plaque is formed.

A typical disadvantage of known dental preparations is that only a relatively short time during which the teeth are being cleaned or the mouth is being rinsed is available for antimicrobial agents in the preparations to take effect. The problem is compounded by the fact that dentifrice preparations are used infrequently; most are used once or, perhaps, twice daily. Consequently, the long time period between brushings for a majority of the population provides optimum plaque forming conditions.

In many other personal and household applications, it would be desirable to provide enhanced surface substantivity Laundry detergents, for example, would benefit by mcreasmg perfume substantivity on fabrics so as to provide increased perfume impact on clothing after laundering or during use. Increased antimicrobial substantivity would also be beneficial from the viewpoint of reducing malodors associated with sweat or other soils. Enhanced perfume substantivity would also be valuable m fine fragrance and perfumed cosmetics. Enhanced coolant substantivity, on the other hand, would be beneficial in cough/cold products There has been a need, therefore, for developing lipophilic compositions which have improved surface residuality, impact and/or antimicrobial efficacy.

The use of lipophilic compounds such as perfumes, flavorants and the like m bleach-containing compositions can also raise a number of problems, especially loss of perfume or flavorant character or intensity as a result of interaction with the bleach. The efficacy of the bleaching agent can also be adversely effected. It would thus be desirable to improve the stability and effectiveness of bleach compositions containing bleach-sensitive ingredients. 3 It is known to include silicones in dentifrice compositions, allegedly to coat the teeth and prevent cavities and staining For instance, GB-A-689,679 discloses a mouthwash containing an organopolysiloxane for preventing adhesion of, or for removing tars, stams, tartar and food particles from the teeth. The mouthwash may include antiseptic compounds, such as thymol, and flavoring and perfuming agents.

US-A-2,806,814 discloses dental preparations including, in combination, a higher aliphatic acyl amide of an ammo carboxylic acid compound as an active and a silicone compound. The patent notes that silicone compounds have been proposed for prevention of adhesion or to facilitate the removal of tars, stams, tartar and the like from teeth. The silicone compound is said to act as a synergist in improving the antibacterial and acid inhibiting activity of the active ingredient. Dimethyl polysiloxanes are said to be particularly effective. Flavoring oils and/or menthol may be mcluded.

US-A-3624120 discloses quaternary ammonium salts of cyclic siloxane polymers for use as cationic surfactants, bactericides and as anticariogemc agents.

Accordingly, the present invention provides a flavor, perfume, coolant, antimicrobial or other lipophilic composition havmg improved surface-substantivity, impact and/or efficacy.

The invention further provides a bleach composition comprising an inorganic persalt bleaching agent, and a lipophilic compound such as a flavorant and/or perfume and which has improved stability.

SUMMARY OF THE INVENTION According to a first aspect of the invention, there is provided a flavor, perfume, coolant, antimicrobial or other lipophilic composition comprising an aminoalkylsilicone having an aminoalkylsiloxane content of from about 0.1%-2% on a repeating unit basis. 4 The invention also relates to the use of an ammoalkylsilicone with a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof to provide improved surface residuality, wherein the ammoalkylsilicone is selected from aminoalkylsilicones havmg an aminoalkylsiloxane content of from about 0.1 %-2% on a repeating unit basis.

According to a further aspect of the invention, there is provided a bleach composition comprising an inorganic persalt bleaching agent, a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof, and an ammoalkylsilicone having an aminoalkylsiloxane content of from about 0.1 %-2% on a repeating unit basis The invention also relates to the use of an ammoalkylsilicone with an inorganic persalt bleachmg agent and a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof to provide improved lipophile stability, wherein the ammoalkylsilicone is selected from aminoalkylsilicones havmg an aminoalkylsiloxane content of from about 0.1 %-2% on a repeatmg unit basis All percentages and ratios herein are by weight of total composition, unless otherwise indicated.

The compositions of the invention thus comprise an ammoalkylsilicone antiplaque agent and a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof. Other compositions of the mvention take the form of bleach and/or detergent compositions which comprise the ammoalkylsilicone antiplaque agent and lipophile.

In general terms, the ammoalkylsilicone is selected from noncyclic, hydrophobic aminoalkysilicones having a formula comprising two basic units: 1) (R*)m(R)nSiQ(4-m-n)/2 wherein m+n is 1, 2 or 3, n is 1, 2 or 3; m is 0,1,2; and 2) (R*)a(R^)bSiO(4-a-b)/2 wherein a+b is 1, 2, or 3, and a and b are integers, wherein Rl and are independently selected from H ,alkyl and alkenyl of about 1 to about 10 carbons optionally substituted with fluoro or cyano groups, hydroxy, alkoxy, and acetoxy, for example, wherein Rl and R^ are independently selected from methyl, ethyl, phenyl, vmyl, trifluoropropyl and cyanopropyl, and R is R4 R4 — R3-N-R5 or —R3-N-R5 x" ifi wherein R3 is a divalent alkylene of about 1-20, preferably about 3-5 carbon atoms optionally substituted or interrupted by O atoms, R4, R^ and R6 which may be the same or different are selected from H, alkyl of about 1-20, preferably about 1-10, more preferably about 1-4 carbons optionally substituted or interrupted by N and/or O atoms, and X~ is a monovalent anion such as halide, hydroxide, and tosylate, said ammoalkylsilicone mcludmg from about 0.1-2%, preferably from about 0.5-2% of unit (1) on a repeating unit basis.

In a preferred embodiment, the aminoalkylsilicones comprise amodimethicones. Amodimethicones are polydimethylsiloxane polymers containing aminoalkyl groups. The aminoalkyl groups may be present either pendant or at one or more ends of the polydimethylsiloxane cham. Preferred are aminoalkylsilicones m which aminoalkyl moiety R is selected from (CH2)3NH2, (CH2)3NHCH2CH2NH2, (CH2)3N(CH2CH2OH)2, (CH2)3NH3+X-, and (CH2)3N(CH3)2(Ci8H37)+X~, and especially from (CH2)3NH2 and (CH2)3NHCH2CH2NH2- Also preferred are aminoalkyl silicones havmt, an average molecular weight of about 5,000 and above, preferably from about 5000 to about 100,000, more preferably from about 5000 to about 30,000. 6 Ammoalkylsilicone compounds suitable for use herein are well known Methods of preparing aminoalkylsilicones are given m, for example, US-A-2,930,809.

Examples of amodimethicones mclude OSI's Magnasoft fluid. These polymers comprise aminoalkyl groups affixed to a predominantly polydimethylsiloxane structure. The typical structure of Magnasoft1 s aminoalkyl group-containing units is -OSi(Me)C3H6NHCH2CH2NH2.

The ammoalkylsilicone is generally present m a level of from about 0.01% to about 25%, preferably from about 0.1% to about 5%, more preferably from about 0.5 % to about 1.5% by weight.

The compositions of the invention preferably also mclude a lipophilic compound. In general terms, lipophilic compounds suitable for use herein are oil-like materials which are soluble or solubilisable m the ammoalkylsilicone, preferably at a level of at least about 1%, more preferably at least about 5 % by weight at 25°C. Preferred lipophilic compounds are selected from flavorants, perfumes, physiological cooling agents and antimicrobial compounds. The ammoalkylsilicone acts to enhance the substantivity of the lipophilic compound to a surface treated therewith, thereby providing enhanced and/or sustained flavor, perfume or coolant impact and/or antimicrobial efficacy.

Lipophilic flavorants suitable for use herein comprise one or more flavor components selected from wintergreen oil, oregano oil, bay leaf oil, peppermint oil, spearmint oil, clove oil, sage oil, sassafras oil, lemon oil, orange oil, anise oil, benzaldehyde, bitter almond oil, camphor, cedar leaf oil, maijoram oil, citronella oil, lavendar oil, mustard oil, pine oil, pine needle oil, rosemary oil, thyme oil, cinnamon leaf oil, and mixtures thereof.

Lipophilic perfumes suitable for use herein comprise one or more known perfume components mclusive of natural products such as essential oils, absolutes, resins, etc., and synthetic perfume components such as 7 hydrocaibons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitnles etc., including saturated and unsaturated compounds, aliphatic, carboxyhc and heterocyclic compounds Examples of perfume materials suitable for use herein include geranyl acetate, lmalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, terpinyl acetate, tncyclodecenyl acetate, tncyclodecenyl propionate, 2-phenylethyl acetate, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate, methyl dihydrojasmonate, phenoxyethyl isobutyrate, neryl acetate, tnchloromethyl-phenylcarbinyl acetate, p-tertiary butyl-cyclohexyl acetate, isononyl acetate, cedryl acetate, vetiveryl acetate, benzyl alcohol, 2-phenylethanol, hnalool, tetrahydrolmalool, citronellol, dimethylbenzylcarbmol, dihydromyrcenol, tetrahydromyrcenol, terpineol, eugenol, geraniol, vetiverol, 3-isocamphyl-cyclohexanol, 2-methyl-3-(p-tertiary butylphenyl)-propanol, 2-methyl-3 -(p-isopropylphenyl)-propanol, 3-(p-tertiary butylphenyl)-propanol, nerol, alpha-n-amylcmnamic aldehyde, alpha-hexyl-cinnamic aldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, hydroxycitronellal, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitnle, citronellonitrile, cedryl methyl ether, isolongifolanone, aubepine mtnle, aubepme, heliotropme, coumarin, vanillm, diphenyl oxide, lonones, methyl lonones, isomethyl lonones, irones, cis-3-hexenol and esters thereof, indane musks, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brassylate, aromatic mtromusks and mixtures thereof.

Lipophilic antimicrobial compounds suitable for use herein mclude thymol, menthol, triclosan, 4-hexylresorcinol, phenol, eucalyptol, benzoic acid, benzoyl peroxide, butyl paraben, methyl paraben, propyl paraben, salicylamides, and mixtures thereof.

Physiological coolmg agent suitable for use herein mclude carboxamides, menthane esters and menthane ethers, and mixtures thereof.

Suitable menthane ethers for use herem are selected from those with the formula: 8 -X or5 where R5 is an optionally hydroxy substituted aliphatic radical containing up to 25 carbon atoms, preferably up to 5 carbon atoms, and where X is hydrogen or hydroxy, such as those commercially available under the trade name Takasago, from Takasago International Corporation. A particularly preferred cooling agent for use in the compositions of the present invention is Takasago 10 [3-1-menthoxy propan-l,2-diol (MPD)]. MPD is a monoglycerm derivative of 1-menthol and has excellent coolmg activity.

The carboxamides found most useful are those described m US-A-4,136,163, January 23, 1979 to Wason et al, and US-A-4,230, 688, October 28, 1980 to Rawsell et al.

The level of lipophilic compound in the compositions of the invention is generally in the range from about 0 01 % to about 10%, preferably from about 0.05% to about 5%, more preferably from about 0.1 % to about 3% by weight.

The compositions of the invention optionally include one or more surfactants, these bemg especially preferred m lipophilic compositions of the mvention for the purpose of solubilization of the lipophile and for providing improved efficacy. Suitable surfactants include non-soap anionic, nomonic, catiomc, zwitterionic and amphoteric orgamc synthetic detergents. Many of these suitable agents are disclosed by Gieske et al. m US-A-4,051,234, September 27, 1977.

Examples of surfactants suitable for use herein include Cg-Cig alkyl sulfates and alkyl ether sulfates ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per mole; anionic sulfonates mclusive of C5- 9 C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxyhc acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, and mixtures thereof; anionic carboxylates inclusive of primary and secondary Cfi to Cjg alkyl carboxylate, ethoxy carboxylate and polyethoxy polycarboxylate surfactants having an average degree of ethoxylation of from about 0 to about 10, C5-C17 sarcosinates such as sodium cocoylsarcosmate, sodium lauroyl sarcosmate (Hamposyl-95 ex W. R. Grace); condensation products of ethylene or propylene oxide with fatty acids, fatty alcohols, fatty amides, polyhydnc alcohols (e.g. sorbitan monostearate, sorbitan oleate), alkyl phenols (e.g Tergitol) and polypropyleneoxide or polyoxybutylene (e.g. Pluronics); alkylpolysaccharides as disclosed m US-A-4,565,647; amine oxides such as dimethyl cocamine oxide, dimethyl lauryl amine oxide and cocoalkyldimethyl amrne oxide (Aromox); polysorbates such as Tween 40 and Tween 80 (Hercules); sorbitan stearates, sorbitan monooleate, etc; cationic surfactants such as cetyl pyridinium chloride, cetyl trimethyl ammomum bromide, di-isobutyl phenoxy ethoxy ethyl-dimethyl benzyl ammonium chloride and coconut alkyl trimethyl ammonium nitrate.

Highly preferred herein from the view point of lipophile solubilization are the nomonic surfactants One class of nomonic surfactant suitable for use herein are those havmg the general formula: in which Rj is an alk(en)yl or aik(en)yl phenyl group havmg 8 to 22, preferably 10 to 20 carbon atoms ion the alk(en)yl moiety and m and n represent weight-averages in the range 0-80 and 2-80 respectively Shorter chain length alkyl groups are generally to be avoided for efficacy reasons and because unreacted fatty alcohol m such surfactants is a source of malodour and occasionally of skin irritation. It will be understood that surfactants of this type are usually mixtures of varying degrees of ethoxylation / propoxylation, accordingly m and n represent the respective weight-averages of the number of propoxylate and ethoxylate PCTAJS95/15766 groups. Nomonic surfactants of the above general type include mixed alkoxylates in which ro and n are both m the range from about 2 to about 80, with m preferably being m the range from about 2 to about 20, more preferably from about 3 to about 10 and with n preferably being in the range from about 2 to about 60, more preferably from about 5 to about 50 One such material is PPG-5-ceteth-20 (available from Croda Inc as Procetyl AWS), whei- m and n have the values 5 and 20 respectively Other suitable nomonic surfactants include polyethoxylated surfactants, e.g. ethoxylated alKylphenol ethers, particularly octyl- and nonylphenol ethers containing 8-16 EO; ethoxylated aliphatic Cg-C20 alcohols, which may be linear or branched and contain 8-16, preferably 9-15 EO; and ethoxylated hydrogenated castor oils.

In general, the ratio of surfactant to the perfume, coolant or other oily material will be in the range of from about 50:1 to about 1.10, preferably from about 20:1 to about 1:2, more preferably from about 10*1 to about 1:1.

Bleaching compositions of the invention additionally mclude one or more bleaching agents optionally together with organic peroxyacid precursors, effervescence generators, chelating agents, etc The bleaching agent takes the form of an inorganic persalt and can be selected from any of the well-known bleaching agents known for use in household bleaches, detergents, denture cleansers and the like such as the alkali metal and ammonium persulfates, perborates inclusive of mono-and tetrahydrates, percarbonates (optionally coated as described in GB-A-1,466,799) and perphosphates and the alkali metal and alkaline earth metal peroxides. Examples of suitable bleaching agents mclude potassium, ammomum, sodium and lithium persulfates and perborate mono- and tetrahydrates, sodium pyrophosphate peroxyhydrate and magnesium, calcium, strontium and zinc peroxides. Of these, however, the alkali metal persulfates, perborates, percarbonates and mixtures thereof are prefered for use herein, highly preferred being the alkali metal perborates and percarbonates. 11 The amount of bleaching agent in the bleaching compositions of the invention is generally from about 5 to about 70% preferably from about 10% to about 50%.

The bleaching compositions can also incorporate an effervescence generator which in preferred embodiments takes the form of a solid base material which in the presence of water releases carbon dioxide or oxygen with effervescence. The effervescence generator can be selected from generators which are effective under acid, neutral or alkaline pH conditions, but preferably it consists of a combination of a generator which is effective or most effective under acid or neutral pH conditions and a generator which is effective or most effective under alkaline pH conditions. Effervescence generators which are effective under acid or neutral pH conditions include a combination of at least one alkali metal carbonate or bicarbonate, such as sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, potassium carbonate, potassium bicarbonate, or mixtures thereof, in admixture with at least one non-toxic, physiologically-acceptable organic acid, such as tartaric, fumanc, citric, malic, maleic, glucomc, succinic, salicylic, adipic or sulphamic acid, sodium fumarate, sodium or potassium acid phosphates, betaine hydrochloride or mixtures thereof. Of these, malic acid is preferred Effervescence generators which are effective under alkaline pH conditions mclude persalts such as alkali and alkaline earth metal peroxoborates as well as perborates, persulphates, percarbonates, perphosphates and mixtures thereof as previously described, for example, a mixture of an alkali metal perborate (anhydrous, mono- or tetrahydrate) with a monopersulphate such as Caroat R marketed by E I du Point de Nemours Co. and which is a 2:1:1 mixture of monopersulphate, potassium sulphate and potassium bisulphate and which has an active oxygen content of about 4.5%.

In preferred bleaching compositions suitable for use as denture cleansers, the solid base material incorporates a (bi)carbonate/acid effervescent couple optionally in combination with a perborate/persulphate oxygen effervescence generator. The combination of generators is valuable for achieving optimum dissolution characteristics and pH conditions for achieving optimum cleaning and antimicrobial activity. The (bi)carbonate 12 components generally comprise from about 5% to about 65%, preferably from about 25 % to 55 % of the total composition; the acid components generally comprise from about 5% to about 50%, preferably from about 10% to about 30% of the total composition.

The bleachmg compositions of the invention can be supplemented by other known components of such formulations. An especially preferred additional component is an organic peroxyacid precursor, which in general terms can be defined as a compound having a titre of at least 1.5ml of 0.1N sodium thiosulfate m the following peracid formation test.

A test solution is prepared by dissolving the following materials in 1000 mis distilled water: sodium pyrophosphate (Na4P207.10H20) 2.5g sodium perborate (NaBO2.H2O2.3H2O) havmg 10.4% available oxygen 0.615g sodium dodecylbenzene sulphonate 0.5g To this solution at 60°C an amount of activator is added such that for each atom of available oxygen present one molecular equivalent of activator is introduced.

The mixture obtained by addition of the activator is vigorously stirred and maintained at 60°C. After 5 minutes from addition, a 100 ml portion of the solution is withdrawn and immediately pipetted onto a mixture of 250 g cracked ice and 15 ml glacial acetic acid. Potassium iodide (0.4 g) is then added and the liberated iodine is immediately titrated with 0.1 N sodium thiosulphate with starch as indicator until the first disappearance of the blue colour. The amount of sodium thiosulphate solution used in ml is the titre of the bleach activator.

The organic peracid precursors are typically compounds containing one or more acyl groups, which are susceptible to perhydrolysis. The preferred PCIYUS95/15766 13 activators are those of the N-acyl or O-acyl compound type containing a acyl radical R-CO wherem R is a hydrocarbon or substituted hydrocarbon group having preferably from about 1 to about 20 carbon atoms.

Examples of suitable peracid precursors include: 1) Acyl organoamides of the formula RCONR1R2, where RCO is carboxylic acyl radical, Rj is an acyl radical and R2 is an organic radical, as disclosed in US-A-3,117,148. Examples of compounds falling under this group include: a) N,N - diacetylaniline and N-acetylphthalimide; b) N-acylhydantoms, such as N,N' -diacetyl-5,5-dimethylhydantoin; c) Polyacylated alkylene diamines, such as N,N,N'N' -tetraacetylethylenediamine (TAED) and the corresponding hexamethylenediamine (TAHD) derivatives, as disclosed in GB-A-907,356, GB-A-907,357 and GB-A-907,358; d) Acylated glycolunls, such as tetraacetylglycolunl, as disclosed in GB-A-1,246,338, GB-A-1,246,339 and GB-A-1,247,429. 2) Acylated sulphonamides, such as N-methyl-N-benzoyl-menthane sulphonamide and N-phenyl-N-acetyl menthane sulphonamide, as disclosed m GB-A-3,183,266. 3) Carboxylic esters as disclosed m GB-A-836,988, GB-A-963,135 and GB-A-1,147,871. Examples of compounds of this type include phenyl acetate, sodium acetoxy benzene sulphonate, trichloroethylacetate, sorbitol hexaacetate, fructose pentaacetate, p-nitrobenzaldehyde diacetate, isopropeneyl acetate, acetyl aceto hydroxamic acid, and acetyl salicylic acid. Other examples are esters of a phenol or substituted phenol with an alpha-chlorinated lower aliphatic carboxylic acid, such as chloroacetylphenol and chloroacetylsalicylic acid, as disclosed in US-A-3,130,165. 4) Carboxylic esters havmg the gernal formal Ac L wherein Ac is the acyl moiety of an organic carboxylic acid comprising an optionally ^ WO 96/19194 PCI7US95/15766 14 substituted, linear or branched C6-C20 alkyl or alkenyl moiety or a C6-C20 alky 1-substitu ted aryl moiety and L is a leaving group, the conjugate acid of which has a pKa m the range from 4 to 13, for example oxybenzenesulfonate or oxybenzoate. Preferred compounds of this type are those wherein: a) Ac is R3-CO and R3 is a linear or branched alkyl group containing from 6 to 20, preferably 6 to 12, more preferably 7 to 9 carbon atoms and wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 5 to 18, preferably 5 to 10 carbon atoms, R3 optionally being substituted (preferably alpha to the carbonyl moiety) by CI, Br, OCH3 or OC2H5. Examples of this class of material include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5-tnmethylhexanoyloxybenzoate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxybenezenesulfonate, the acyloxy group in each instance preferably being p-substituted; b) Ac has the formula R3(AO)mXA wherein R3 is a lmear or branched alkyl or alkylaryl group containing from 6 to 20, preferably from 6 to 15 carbon atoms m the alkyl moiety, R5 bemg optionally substituted by CI, Br, OCH3, or OC2H5, AO is oxyethylene or oxypropylene, m is from 0 to 100, X is O, NR4 or CO-NR4, and A is CO, CO-CO, R^-CO, CO-R^-CO, or CO-NR4-R5-CO wherein R4 is C1-C4 alkyl and R5 is alkylene, alkenylene, arylene or alkarylene containing from 1 to 8 carbon atoms m the alkylene or alkenylene moiety.

Bleach activator compounds of this type include carbonic acid derivatives of the formula R3(AO)mOCOL, succinic acid derivatives of the formula R30C0(CH2)2C0L, glycollic acid derivatives of the formula R3OCH2COL, hydroxypropionic acid derivatives of the formula R3OCH2CH2COL, oxalic acid derivatives of the formula R3OCOCOL, maleic and fumaric acid derivatives of the formula R30C0CH=CHC0L, acyl aminocaproic acid derivatives of the formula R3CONRj(CH2)6COL, acyl glycine derivatives of the formula R3CONR1CH2COL, and ammo-6-oxocaproic acid derivatives of the formula R3N(Ri)CO(CHo)4COL. In the above, m is preferably from 0 to 10, and R3 is preferably Cfr C12, more preferably C6-C10 alkyl when m is zero and Cg-C15 when m is non-zero The leaving group L is as defined above.

) Acyl-cyanurates, such as triacetyl- or tnbenzoylcyanurates, as disclosed in US patent specification No. 3,332,882. 6) Optionally substituted anhydrides of benzoic or phthalic acid, for example, benzoic anhydride, m-chlorobenzoic anhydride and phthalic anhydride. 7) N-acylated precursor compounds of the lactam class as disclosed generally in GB-A-855735, especially caprolactams and valerolactams such as benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogs such as the chloro, ammo, alkyl, aryl and alkoxy derivatives.

Of all the above, preferred are orgamc peracid precursors of types 1(c), 4(a) and 7.

Where present, the level of peroxyacid bleach precursor by weight of the total composition is preferably from about 0.1% to about 10%, more preferably from about 0.5 % to about 5 % and is generally added in the form of a bleach precursor agglomerate.

The bleach precursor agglomerates preferred for use herein generally comprise a binder or agglomerating agent m a level of from about 5 % to about 40%, more especially from about 10% to about 30% by weight thereof. Suitable agglomerating agents include polyvinylpyrrolidone, poly (oxyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowax havmg a molecular weight of from 4000 to 20,000, nonionic surfactants, fatty acids, sodium carboxymethyl cellulose, gelatin, fatty alcohols, phosphates and polyphosphates, clays, alummosilicates and polymeric 16 polycarboxylates. Of the above, polyethyleneglycols are highly preferred, especially those having molecular weight of from about 1,000 to about 30,000, preferably 2000 to about 10,000.

Preferred from the viewpoint of optimum dissolution and pH characteristics are bleach precursor agglomerates which comprise from about 10% to about 75 %, preferably from about 20% to about 60% by weight thereof of peroxyacid bleach precursor, from about 5 % to about 60% preferably from about 5% to about 50%, more preferably from about 10% to about 40% of a (bi) carbonate/acid effervescent couple, from about 0% to about 20% of a peroxoboroate, and from about 5% to about 40%, preferably from about 10% to about 30% of an agglomerating agent. The final bleach precursor granules desirably have an average particle size of from about 500 to about 1500, preferably from about 500 to about 1,000 um, this bemg valuable from the viewpoint of optimum dissolution performance and aesthetics. The level of bleach precursor agglomerates, moreover, is preferably from about 1% to about 20%, more preferably from about 5% to about 15% by weight of composition.

The bleaching compositions of the invention can be m paste, tablet, granular or powder form. Compositions in tablet form can be smgle or multiple layered tablets.

Bleaching compositions of the invention can be supplemented by other usual components of such formulations, especially surfactants as generally described above, chelating agents, enzymes, dyestuffs, sweeteners, tablet binders and fillers, foam depressants such as dimethylpolysiloxanes, foam stabilizers such as the fatty acid sugar esters, preservatives, lubricants such as talc, magnesium stearate, finely divided amorphous pyrogenic silicas, etc.

Tablet binders and fillers suitable for use herein mclude polyvinylpyrrolidone, poly (oxyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowax having a molecular weight of from 4000 to 20,000, nonionic surfactants, fatty acids, sodium carboxymethyl cellulose, gelatm, fatty alcohols, clays, polymeric polycarboxylates, sodium 17 carbonate, calcium carbonate, calcium hydroxide, magnesium oxide, magnesium hydroxide carbonate, sodium sulfate, proteins, cellulose ethers, cellulose esters, polyvinyl alcohol, alginic acid esters, vegetable fatty materials of a pseudocolloidal character. Of the above, polyethyleneglycols are highly preferred, especially those having molecular weight of from about 1,000 to about 30,000, preferably from about 12,000 to about 30,000.

Chelatmg agents beneficially aid cleaning and bleach stability by keeping metal ions, such as calcium, magnesium, and heavy metal cations in solution. Examples of suitable chelating agents include sodium tripolyphosphate, sodium acid pyrophosphate, tetiasodium pyrophosphate, aminopolycarboxylates such as nitrilotriacetic acid and ethylenediamme tetracetic acid and salts thereof, ethylenediamine-N,N'-disuccimc acid (EDDS) and salts thereof, and polyphosphonates and ammopolyphosphonates such as hydroxyethanediphosphonic acid, ethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and salts thereof The chelatmg agent selected is not critical except that it must be compatible with the other ingredients of the denture cleanser when in the dry state and in aqueous solution Advantageously, the chelatmg agent comprises between 0.1 and 60 percent by weight of the composition and preferably between 0.5 and 30 percent. Phosphonic acid chelatmg agents, however, preferably comprise from about 0.1 to about 1 percent, preferably from about 0.1% to about 0.5 % by weight of composition.

Enzymes suitable for use herein are exemplified by proteases, alkalases, amylases, fungal and bacterial lipases, dextranases, mutanases, glucanases, esterases, cellulases, pectmases, lactases and peroxidases, etc. Suitable enzymes are discussed m US-A-3,519,570 and US-A-3,533,139.

The following Examples further describe and demonstrate the preferred embodiments within the scope of the present invention. 18 EXAMPLES I TO V The following are representative denture cleansing tablets according to the invention. The percentages are by weight of the total tablet. The tablets are made by compressing a mixture of the granulated components in a punch and dye tabletting press at a pressure of about 10^ kPa.

I II m IV V Malic Acid 12 - 14 Citric Acid - - - Sodium Carbonate 8 6 Sulphamic Acid - - 3 3 PEG 20,000 - 3 7 8 PVP 40,000 6 3 - - - Sodium Bicarbonate 23 24 23 24 Sodium Perborate Monohydrate 12 16 Potassium Monopersulphate 18 13 - 14 Pyrogenic Silica - 3 1 1 - Talc 2 - - - - EDTA - 3 EDTMPl 1 - Flavor^ 2 1 2 1 2 Magnasoft Fluid4 1 1.5 0.5 2 1 Bleach Precursor Agglomerate 9 8 12 Bleach Precursor Agglomerate I II in IV V TAED2 2 - 4 2.5 TMHOS3 2 3 - - - Sulphamic Acid 2 2 2 2 3.5 Sodium Bicarbonate 0.5 0.2 0.2 0.5 2 PEG 6000 2.5 2 2.4 2.5 1.5 Dye - 0.8 1.4 2 0.5 1. Ethylenediaminetetramethylenephosphonic acid 2. Tetraacetylethylene diamine 3. Sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate 4. Magnasoft Fluid - supplied by OSI 5 Peppermint-based flavor

Claims (3)

WO 96/19194 PCT/US95/15766 19 In Examples I to V above, the overall tablet weight is 3 g; diameter 25 mm. The denture cleansing tablets of Examples I to V display improved antiplaque,cleansing and anti-bacterial activity together with excellent cohesion and other physical and in-use performance characteristics. EXAMPLES VI TO IX The following are representative perfume, flavour, coolant and antimicrobial compositions according to the invention. The percentages are by weight of total composition. vi vn Vffl IX PPG-5-ceteth-20 3.0 3.0 4.5 3.0 PEG-40 hydrogenated castor - 1.8 4.5 3.0 oil Trideceth-12 2.0 Trideceth-9 - 2.0 - 3.0 Flavor^ 2.0 3.0 Perfume^ - 3.0 Trimethyl butanamide 0.3 0.5 Triclosan - - 1.0 0.5 Magnasoft Fluid4 1.0 1.5 5.0 1.0 Water < to 100% > 6. Perfume is a complex mixture of ingredients used primarily for olfactory purposes. The perfume, flavor, coolant and/or antimicrobial compositions of Examples VI to IX display improved surface-substantivity, impact and/or efficacy. WO 96/19194 PCTAJS95/15766 CLAIMS

1. A flavor, perfume, coolant or antimicrobial composition comprising an ammoalkylsilicone havmg an aminoalkylsiloxane content of from about 0 1 %-2% on a repeating unit basis.

2. A composition according to Claim 1 wherein the ammoalkylsilicone is a noncyclic, hydrophobic ammoalkylsilicone having a formula comprising two basic units: 1) (R*)m(R)nSiO(4-m.n)/2 wherem m+n is 1, 2 or 3; n is 1, 2 or 3; m is 0,l,2;and 2) (R*)a(R^)bSiO(4-a-b)/2 wherem a+b is 1, 2, or 3, and a and b are integers, wherein R* and R2 are independently selected from H, alkyl and alkenyl of about 1 to about 10 carbons optionally substituted with fluoro or cyano groups, hydroxy, alkoxy, and acetoxy, and R is R4 R4 — R3-N-R5 or —R3-N-R5 X~ R6 wherein R3 is a divalent alkylene of about 1-20 carbon atoms optionally substituted or interrupted by O atoms, R^, r5 and R*> which may be the same or different are selected from H, alkyl of about 1-20 carbons optionally substituted or interrupted by N and/or O atoms, and X" is a monovalent anion, said aminoalkyl silicone including about 0.1 %-2% of unit (1) on a repeating unit basis.

3. A composition according to Claim 2 wherein the aminoalkyl silicone has a molecular weight of at least about 5,000 A composition according to Claim 3 wherein the aminoalkyl silicone has a molecular weight from about 5,000 to about 100,000 INTELLECTUAL PROPERTY OFFICE] OF NZ \ - SEP 1399 RECEIVED WO 96/19194 21 PCT/US95/15766 5 A composition according to any of Claims 1 to 4 comprising from about 0 01% to about 25% by weight of the aminoalkyl 6 A composition according to Claim 5 comprising from about 0 1% to about 5% by weight of the aminoalkyl silicone 7 A flavorant composition according to any of Claims 1 to 6 comprising one or more flavor components selected from wmtergreen oil, oregano oil, bay leaf oil, peppermint oil, spearmint oil, clove oil, sage oil, sassafras oil, lemon oil, orange oil, anise oil, benzaldehyde, bitter almond oil, camphor, cedar leaf oil, marjoram oil, citronella oil, lavendar oil, mustard oil, pine oil, pine needle oil, rosemary oil, thyme oil, cinnamon leaf oil, and mixtures thereof. 8 A perfume composition according to any of Claims 1 to 6 compnsmg one or more perfume components selected from geranyl acetate, linalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, terpinyl acetate, tncyclodecenyl acetate, tncyclodecenyl propionate, 2-phenylethyl acetate, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate, methyl dihydrojasmonate, phenoxyethyl isobutyrate, neryl acetate, tnchloromethyl-phenylcarbmyl acetate, p-tertiary butyl-cyclobexyl acetate, isononyl acetate, cedryl acetate, vetuveryl acetate, benzyl alcohol, 2-phenylethanol. Iwialooi, tetrahydrolinalool, citronellol, djrncthyibenzylcarbmol, dihydromyrcenol, tetrahydromyrcenol, terpineol, eugenol, geraniol, vedverol, 3-isocamphyl-cyclohexanol, 2-methyl-3-<p-tertiary butylphenyl)-propanol, 2-methyl-3-(p-isopropylphenyl)-propanol, 3-(p-tertiary butylphenyl)-propanol, nerol, alpha-n-amylcinnamic aldehyde, alpha-hexyl-cinnamic aldehyde, 4-{4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-penteny I)-3-cyclohexenecarbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, hydroxycitronellal, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitrile, silicone WO 96/19194 22 PCT/US95/15766 citronellonitrile, cedryl methyl ether, isolongifolanone, aubepine nitrilc, aubepine, heliotropine, coumarm, vanillin, diphenyl oxide, ionones, methyl lonones, isomethyl ionones, irones, cis-3-bexenol and esters thereof, indane musks, tetralin musks, isochroman musks, macrocychc ketones, macrolactone musks, ethylene brassylate, aromatic nitromusks and mixtures thereof 9 Use of an aminoalkylsilicone with a lipophile selected from flavorants, perfumes, physiological coolants and antimicrobial agents to provide improved surface residuality, wherein the ammoalkylsilicone is selected from aminoalkylsilicones having an aminoalkylsiloxane content of from about 0.1 %-2% on a repeating unit basis. 10 A composition according to Claim 1 and substantially as herein described with reference to any embodiment disclosed 11 Use according to Claim 9 and substantially as herein described with reference to any embodiment disclosed see also complete specification END OF CLAIMS INTELLECTUAL PROPERTY OFFICE OF NZ 1 ~ SEP 1999 RECEIVED