CA2206401A1

CA2206401A1 - Silicone compositions

Info

Publication number: CA2206401A1
Application number: CA002206401A
Authority: CA
Inventors: Iain Allan Hughes
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1994-12-22
Filing date: 1995-12-13
Publication date: 1996-06-27
Also published as: CZ190597A3; EP0799299A1; TR199501647A2; KR100239202B1; GB9425926D0; WO1996019561A1; AU4642896A; PL320864A1; NZ301091A; AU710906B2; EP0799299A4; HUT77711A; BR9510308A; MX9704664A; CN1170430A; JPH10511129A; SK83197A3

Abstract

A bleach composition comprising an inorganic persalt bleaching agent, a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof, and a dimethicone copolyol selected from alkyl- and alkoxy-dimethicone copolyols having formula (I) wherein: X is selected from hydrogen, alkyl, alkoxy and acyl groups having from about 1 to about 16 carbon atoms, Y is selected from alkyl and alkoxy groups having from about 8 to about 22 carbon atoms, n is from about 0 to about 200, m is from about 1 to about 40, q is from about 1 to about 100, the molecular weight of the residue (C2H4O-)x(C3H6O-)yX is from about 50 to about 2000, and x and y are such that the weight ratio of oxyethylene: oxypropylene is from about 100:0 to about 0:100. The composition provides improved lipophile and bleach stability.

Description

W O96119S61 PCT~US9S/16672 SILICONE COMPQSITIONS
,.
TECHNICAL FIELD

The present invention relates to silicone-cont~ininE compositions and to use thereof in various household products such as personal care products, laundry and household cleaners, ble~rhin~ compositions and the like. In particular, it relates to silicone-cont~inin~ lipophilic compositiorls based on flavorants, perfumes, coolants or ~ntimicrobial agents as lipophile and which display improved residuality, impact and/or efficacy on surfaces treated therewith, for e~cample teeth, dentures, skin, hair, lau~dry, dishware, working surfaces and the like.
In addition, it relates to silicone-cont~inin~ bleach compositions which additionally contain bleach-sensitive ingredients suchL as perfumes, flavorants and the like and which display improved stability.

Lipophilic compositions such as flavor, perfume, coolant and disinfectant compositions are widely used either directly or in a variety of household products inclusive of cosmetics, oral and denture compositions, bleach, dishwashing, hard surface cle~nin~ and laundry detergent products, etc. A common problem encountered with lipophilic compositions is that of improving surface subs~tivi~y or re~idll~lity of the lipophilic component. It would be desirable in many if not most household applications to e~h~nce the surface resi~ ty of ~e hpophile m order, for e~ca~mple, to provide increased flavor or perfume impact or increased antimicrobial efficacy.

Modern den~al hygiene and denture preparations, for e~cample, ~ typically contain antiplaque and/or auli~r 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 lr~ed in the film to prevent further ~lG~vlh and metabolism. Flavorants may alleviate the problem of bad breath via a deodorizing action. Some ?ntimicrobial W O96/19S61 PCTnUS9S/16672 agents, e.g. menthol may, also serve as breath deodorizers. However, the efficacy of antimicrobial agents depends largely on their intraoral/denture retention, particularly their retention on the surface of the teeth or dentures where plaque is formed.

A typï~cal 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 bn~sh;n~ for a majority of the population provides optimum plaque forming conditions.

In many other personal and household applications, it would be desirable to provide enh~nced surface subs~llivily. ~.~lln-lry detergents, for e~ample, would benefit by increasing perfume substantivity on fabrics so as to provide increased perfume impact on clothing after l~lln-lering or during use. Increased antimicrobial sub~ ivily would also be beneficial from the viewpoint of reducing malodors associated with sweat or other soils. Fnh~nced perfume subs~tivily would also be valuable in fine fragrance and perfumed cosmetics. Fnh~nced coolant sub~lLivily, 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 resi~ lity, impact and/or antim~icrobial efficacy.

The use of lipophilic compounds such as perfilmes, flavorants and the like in bleach-cont~inin~ 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 ,rove the stability and effectiveness of bleach compositions cont~ininP~ bleach-sensitive ingredients.

It is known to include silicones in dentifrice composntions, allegedly to coat the teeth and prevent cavities and st~inin~. For in~t~n~'e, GB-A-4 689,679 discloses a mouthwash cont~ining an organopolysilo;~ane for preventing adhesion of, or for removing tars, stains, tartar and food particles from the teeth. The mouthwash may includle antiseptic compounds, such as thymol, and flavoring and perfuming agents.

US-~-2,806,814 discloses dental preparations including, in combination, a higher aliphatic acyl amide of an amino carbo~ylic 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, stains, 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 polysilo~anes are said to be particularly efiFective. Flavoring oils and/or menthol may be included.

US-A-3624120 discloses quaternaly ~mmonil~m salts of cyclic silo~cane polymers for use as cationic surfactants, bactericides and as anticariogenic agents.

Accordingly, the present invention provides a flavor~ perfume, coolant, antimicrobial or other lipophilic composition having improved surface-subsL~tivi~y, imp~ct 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.

SUMM[ARY OF THE INVENTIC)N

According to a first aspect of the invention, there is provided a flavor, perfume, coolant, antimicrobial or other lipophilic compos;L;o~
comprising a dimethicone copolyol selected from alkyl- and alko~cy-~limethicone copolyols having the formula (1):

W O96/19561 PCTrUS95116672 l H3 IH3 l H3 fH3- ~H3 CH~- SiO SiO SiO Si~Si- CH3 CH3 CH3 (CH2)3 CH3 n ¦
- - o tC2H40-)x(c3H6o-)yx q -m wherein X is selected from hydrogen, alkyl, alko~cy and acyl groups having from about 1 to about 16 carbon atoms, Y is selected from alkyl and alko~y groups having from about 8 to about 22 carbon atoms, n is from about 0 to about 200, m is from about 1 to about 40, q is fiom about 1 to about 100, the molecular weight of the residue ~C2H4O-)~(c3H6o-)yx is from about 50 to about 2000, ~referably from about 250 to about 1000 and ~ and y are such that the weight ratio of o~yethylene:o~ypropylene is from about 100:0 to about 0:100, preferably from about 100:0 to about 20:80.

The imvention also relates to the use of a dimethicone copolyol with a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mi~tures thereof to provide improved surface residuality, wherein the dimethicone copolyol is selected from alkyl-and àlko~cy-dimethicone copolyols having the formula (1).

Accolrding 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 mi~ res thereof, and a ~iimethicone copolyol selected from alkyl- and alko~cy-~ thicone copolyols having the formula (I):

W ~96/19S61 P ~ AUS9~16672 fH3IH3 fH3 ¦ H3 fH3 C~ SiO SiO SiO SiO--Si--CH3 CH3 CH3 ((~H2)3 CH3 n ¦
- - o (C2H4o-)x(c3H6o-)yx q -m wherein X is selected from hydrogen, alkyl, alko~cy and acyl groups having from about 1 to about 16 carbon atoms, Y is selected from alkyl and alko~cy groups having frorn about 8 to about 22 carbon atoms, n is from about 0 to about 200, m is from about 1 to about 40, q is from about 1 to about 100, the molecular weight of the residue (C2H40-)~c(c3H6o-)yx is from about 50 to about 2000, and ~c and y are such that the weight ratio of o~yethylene:o~cypropylene is from about 100:0 to about 0:100.

The invention also rela~es to the use of a dimethicone copolyol with an inorganic persalt bleaching agent and a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mi~ctures thereof to provide improved lipophile stability, wherein the methicone copolyol is selected from alkyl- and alko~y-~im~thicone copolyols having the formula (I).

Al î pelce~-t~ges and ratios herein are by weight of total composition, unless otherwise indicated.

The compositions of the invention thus comprise a ~limetllicone copolyol antiplaque agent and a lipophile selected from flavorants, perfumes, physiological coolants, ~ntimicrobial agents and mi~ctures thereof. Other compositions of the invention take the form of bleach and/or detergellt compositions which comprise the dimethicone copolyol antiplaque agent and lipophile.

W O96/19S61 PCTrUS95/16672 In general terms, the ~limethicone copolyol is selected from alkyl- and alko7cy-dimethicone copolyols having the formula (I):

l H3IH3 fH3 ¦ f C~--SiO SiO SiO ~ Si- CH3 CH3 CH3 (CH2)3 Y CH3 n ¦
- - o (C2H40-)X(C3H60-)yx q -m wherein X is selected from hydrogen, alkyl, alko~cy and acyl groups having from about 1 to about 16 carbon atoms, Y is selected from alkyl and alko~y groups having from about 8 to about 22 carbon atoms, n is from about 0 to about 200, m is from about 1 to about 40, q is from about 1 to about 100, the molecular weight of the residue (C2H4O-)~c(c3H6o-)yx is from about 50 to about 2000, prefelably from about 250 to about 1000 and ~c and y are such that the weight ratio of o~yethylene:o~ypropylene is from about 100:0 to about 0:100, ,referably from about 100:0 to about 20:80.

In ~refered emb~lim~-nt~, the ~im~.thicone copolyol is selected from C12 to C20 alkyl ~limet~licone copolyols and mi~ctures thereof. Highly pfefell~l is cetyl rlimethicone copolyol marketed under the Trade Name Abil EM90. The ~limetllicone copolyol is generally present in a level of from about 0.01% to about 25 %, ~refelably from about 0.1 ~o to about 5 %, more l~referably from about 0.5% to about 1.5% by weight.

The compositions of the invention prefelably also include a lipophilic ~ compound. In general terms, lipophilic compounds suitable for use herei.n are oil-like materials which are soluble or solubilisable in the dimethicone copolyol, prefer~bly at a level of at least about 1%, more ~refelably at least about 5% by weight at 25~C. r~efelled lipophilic W ~ 96/19~61 PCTnUS95116672 compounds are selected from flavorants, perfumes, physiological cooling agents and antimicrobial compounds. The ~limethicone copolyol acts to enhance the substantivity of the lipolphilic compound to a surface treated therewith, thereby providing enhanced andtor sl-ct~in~d flavor, perfume or coolant impact and/or antimicrobial efficacy.

Lipophilic flavorants suitable for use herein comprise one or more flavor components selec~ed from wintergreen oil, oregano oil, bay leaf oil, peppermint oil, spearmint oil, clove oil, sage oil, s~ fras oil, lemon oil, orange oil, anise oil, be~ ehyde, 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 mi~ctures thereof.

Lipophilic perfumes suitable for use herein comprise one or more known perfume components inclusive of natural products such as essential oils, absolutes, resins, etc., and synthetic perfume components such as hydrocarbons, alcohols, aldehydLes, ketones, ethers, acids, esters, ~cet~ ketals, nitriles etc., including saturated and l~n~tl~rated compounds, aliphatic, carbo~ylic and heterocyclic compounds. E~amples of perfume materials suitable for use herein include geranyl ~cet~te, linalyl ~cet~te, citronellyl acetate, dihydromyrcenyl ~et~t~, terpinyl ~cet~te, tricyclodecenyl acetate, tricyclodecenyl propionate, 2-phenylethyl ~et~te, benzyl ~cet~te, benzyl salicylate, benzyl ben7o~te, styrallyl ~cet~te, amyl salicyla~e, methyl dihydrojasmonate, pheno~cyethyl isobutyrate, neryl ~et~te~
trichloromethyl-phenylcarbinyl ~cet~te, p-tertiary butyl-cyclohe~yl ~cet~te, isononyl ~cet~e, cedryl ~ret~te, vetiveryl ~cet~te, benzyl alcohol, 2-phenyleth~nol, linalool, tetrahydrolinalool, citronellol, ~imethylbe~lzylcarbinol, dihydromyrcenol, tetrahydromyrcenol, terpineol, eugenol, geraniol, vetiverol, 3-i~oc~mphyl-cyclohe~canol, 2-methyl-3-(p tertiary butylphenyl)-propanol, 2-methyl-3-(p-isopropylphenyl)-propanol, 3-(p-tertiary butylphenyl)-propanol, nerol, alpha-n-amylcinn~mic aldehyde, alpha-he~cyl-cinn~mic aldehyde, ~(~
hydro~cy~methylpentyl)-3-cyclohe~enec~rb~ hyde, ~(~methyl-3-pc.llellyl)-3-cyclohe~cenec~rbaldehyde, ~aceto~cy-3-pentyl-W O96/19S61 PCTrUS9Stl6672 tetrahydropyran, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n--1ec~n~l, n-do~ec~n~l, hydro~ycitronellal, pherlyl~et~l~lehyde dimethyl acetal, phenyl~ce~ lehyde diethyl acetal, geranonitrile, citronellonitrile, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropine, coumarin, v~nillin, diphenyl ,, o~ide, ionones, methyl ionones, isomethyl ionones, irones, cis-3-he~cenol and esters thereof, indane musks, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brassylate, aromatic nitromusks and mi~ctures thereof.

Lipophilic antimicrobial compounds suitable for use herein include thyn~ol, menthol, triclosan, ~he~ylresorcinol, phenol, eucalyptol, benzoic acid, benzoyl pero~cide, butyl paraben, methyl paraben, propyl paraben, salicyl~mi~le~, and mi~ctures thereof.

Physiological cooling agent suitable for use herein include carbo~c~mi~es, menth~nP esters and menth~ne ethers, and mi~ctures thereof.

Suitable menth~ne ethers for use herein are selected from those with the formula:

. , ~

where Rs is an optionally hydro~cy sul)s~ .tP~ aliphatic radical co.~ up to 25 carbon atoms, pler~ably up to 5 carbon atoms, and where X is hydrogen or hydro~y, such as those commercially available under the trade name T~k~ o, from T~k~ o International Corp~oration. A particularly preferred cooling agent for use in the compositions of the present invention is T~k~c~go 10 [3-l-mentho~cy propan-1,2-diol (MPD)]. MPD is a monoglycerin derivative of l-mPn~hol and has e~ccellent cooling activity.
-W ~96119S61 PCTAUS9S/16672 The carbo~amides found most useful are those described in US-A-4,136,163, January 23, 1979 to Wason et al., and US-A-4,230, 688, October 28g 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 ~o to about 10%, preferably from about 0.05 % to about 5 %, more prefe~ably from about 0.1 % to about 3 % by weight.

The compositions of the invention optionally include one or more surf~ct~nts, these being especially plerell~d in lipophilic compositions of the invention for the purpose of solubilization of the lipophile and for providing improved efficacy. Suitable surfactants include non-soap anionic, nonionic, cationic, zwitterionic and amphoteric organic synthetic dPter~c.lts. Many of these suitable agents are disclosed by Gieske et al. in US-A4,051,234, Se~telllber 27, 1977.

E~amples of surf~ct~nt~ suitable for use herein include C6-C1g alkyl slllf~tes and alkyl ether sl)lf~tes ethoxylated with frolm about 0.5 to about 20 moles of ethylene o~cide per mole; anionic sulfonates inclusive of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarbo~cylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, and mi~tures thereof; anionic carbo~cylates inclusive of primary and secondary C6 to C1g alkyl carbo~cylate, etho~cy carbo~cylate and polyetho~cy polycarbo~cylate surf~c~nts having an average degree of etho~cylation of from about 0 to abou~ 10; Cs-C17 sarcosin~te~ such as ~o~ m cocoylsarcosi.~te; so~ m lauroyl sarcosinate (Hamposyl-95 e~c W. R. Grace); con~lenc~tion products of ethylene or propylene o~cide with fatty acids, fatty alcohols, fatty ~mi~leS, polyhydric alcohols (e.g. sorbitan monoste~rate, SOllJikll oleate), alkyl phenols (e.g. Tergitol) and polypropyleneo~ide or polyo~ybutylene (e.g. Pluronics); alkylpolysaccharides as disclosed in US-A~,565,647; amine o~cides such as ~limetllyl coc~mine o~ide, dimethyl lauryl amine o~ide and cocoaLlcylclimet~lyl amine o~cide (Aromo~); polysorbates such as Tween 40 and Tween 80 (Hercules);

W O96/l9S61 PCTnUS9S/16672 sorbitan stearates, sorbitan monooleate, etc; cationic surfactants such as cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, di-isobutyl pheno~cy etho~y ethyl-clim~t~lyl benzyl ammonium chloride and coconut alkyl trimethyl ammonium nitrate.

Highly prefel,~d herein from the view point of lipophile solubilization are the nonionic surfactants. One class of nonionic surfactant suitable for use herein are those having the general formula:

Rl--(O I HCH2)m (OCH2CH2) n OH

in which R1 is an alk(en)yl or alk(en)yl phenyl group having 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 bec~1se unreacted fatty alcohol in such surfact~nt~
is a source of malodour and occasionally of skin irritation. It will be understood that surfactants of this type are usually mi~tures of varying degrees of etho~cylation / propo~tylation, accordingly m and n represent the respective weight-averages of the number of propo~cylate and etho~ylate groups. Nonionic surfactants of the above general type include mi~ted aLko~tylates in which m and n are both in the range from about 2 to about 80, with m y~eferably being in the range from about 2 to about 20, more ~fef~.ably from about 3 to about 10 and with n pr~r~,~bly being in the range from about 2 to about 60, more ,refer~bly from about S to about 50. One such material is PPG-S-cetetlh-20 (available from Croda Inc as Procetyl AWS), where m and n have the values S and 20 respectively. Other suitable nonionic surfactants include polyetho~cylated surfactant~, e.g. etbo~cylated aL~cylphenol ethers, particularly octyl- and nonylphenol ethers cont~inin5~ 8-16 EO; etho~tylated aliphatic Cg-C20 alcohols, which may be linear or branched and contain 8-16, ~lefe~ably 9-15 EO; and ethoxylated hydrog~ated castor oils.

W 096119561 P~ l/V~/16672 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 l~rom about 20:1 to about 1:2, more preferably from about 10:1 to about 1:1.

Bleaching compositions of the invention additionally include one or more bleaching agents optionally together with organic pero~cyacid precursors, effervescence generatols, 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 pers~llf~tec, perborates inclusive of mono-and tetrahydrates~ percarbonaees (optionally coated as described in GB-A-1,466,799) and perphosphates and the alkali metal and z-lk~line earth metal pero~cides. Examples of suitable bleaching agents include potassium, ammonium, sodium and lithillm lpersulfates and perborate mono- and tetrahydrates, sodium pyrophosphate pero~cyhydrate and m~nesillm, calcium, strontium and zinc pero~cides.
Of these, however, the alkali metal persnlf~tçs, perborates, percarbona~es and mi~ctures thereof are prefered for use herein, highly ~rerel,~d being the alkali metal perborates and percarbonates.

The amount of bleaching agent in the bleaching compositions of the invention is generally from about S to about 70% I.refe~ably from about 10% to about 50%.

The ble~-hin~ compositions can also incorporate an effervescence generator which in ~rerer~ed embo~lim~rltc takes the form of a solid base material which in the presence of water releases carbon dioxide or o~cygen with effervescence. The effervescence generator can be selected from generatols which are effective under acid, neutral or ~llr~line pH conditions, but ~refel~bly it concictc 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 ~Ik~linç pH conditions. Effervescence generators which are effective under acid or neutral pH conditions include a combination of at least W O96119561 PCTnUS95/16672 one allkali metal carbonate or bicarbonate, such as sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, potassium carbonate, potassium bicarbonate, or mi~tures thereof, in admi~cture with at least one non-to~cic, physiologically-acceptable organic acid, such as tartaric, fumaric, citric, malic, maleic, gluconic, succinic, salicylic, adipic or sulphamic acid, sodium f~marate, sodium or potassium acid phosphates, betaine hydrochloride or mi~ctures thereof. Of these, malic acid is preferred. Effervescence generators which are effective under ~lk~line pH conditions include persalts such as alkali and ~lk~ e earth metal pero~oborates as well as perborates, persulphates, percarbonates, perphosphates and mi~cbures thereof as previously described, for e~cample, a mi~ture 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 mi~ture of monopersulphate, potassium sulphate and potassium bisulphate and which has an active o~ygen content of about 4.5~.

In prefelled 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 o~cygen effervescence generator. The comb;nation of generators is valuable for achieving optimum dissolution characteristics and pH conditions for achieving optimurn cle~nin~ and antimicrobial activity. The (bi)carbonate components generally comprise from about 5% to about 65%, ple~eiably from about 25 % to 55 % of the total composition; the acid components generally comprise from about 5% to about 50%, ~lefe~ably from about 10% to about 30% of the total composition.

The bleaching compositions of the invention can be supplemented by other known components of such formulations. An especially prefelled additional component is an organic pero~cyacid precursor, which in general terms can be defined as a compound having a titre of at least 1 .Sml of 0. lN sodium thiosulfate in the following peracid formation test.

W O96119561 PCT~US9S~16672 A test solution is prepared by dissolving the following materials in 1000 mls distilled water:

so~ium pyrophosphate (Na4P207. lOH20) 2.5g sodium perborate (NaB02.H202.3H20) having 10.4% available o~ygen 0.615g sodium dodecylbenzene sulphonate 0.5g To this solution at 60~C an amount of ac~i-/ato~ is added such that for each atom of available o~ygen present one molecular equivalent of activator is intro~ ce~l.

The mi~ture obtained by addition of the ac~ivator is vigorously stirred and m~int~ineA at 60~C. After S mimlt~?~ from addition, a 100 ml portion of the solution is withdrawn and imme~ tely pipetted onto a mi~cture of 250 g cracked ice and 15 ml glacial acetic acid. Potassium iodide ~0.4 g) is then added and the liberated iodine is imm~li~tely titrated with 0.1 N co~ m thiosulphate with starch as indicator until the first disappearance of the blue colour. The ~mount of sodium thiosulphate solution used in ml is the titre of the bleach activator.

.
The organic peracid precursors are typically compounds cont~ining one or more acyl groups, which are susceptible to perhydrolysis. The ~rerc;~led activators are those of the N-acyl or 0-acyl compound ~ype co"t~ in~ a acyl radical R-C0 wherein R is a hydrocarbon or substh~lte~l hydroca~l,on group having ~refelably ~rom about 1 to about 20 carbon atoms. F~mples of suitable peracid precursors include:

- 1) Acyl org~no~mi~les of the formula RCONRlR2, where RC0 is carbo~cylic acyl radical, Rl is an acyl radical and R2 is an ~ organic radical, as disclosed in US-A-3,117,148. E~camples of compounds falling under this group include:
a) N,N - diacetyl~niline and N-acetylphth~limi~le, W O96/19S61 PCTrUS95116672 b) N-acylhydantoins, such as N,N ' -diacetyl-5,5-dimethylhydantoin;
c) Polyacylated alkylene ~ min~s~ such as - N,N,N'N' -tetraacetylethylene~i~mine (TAED) and the corresponding he~methylenP,~ mine (TAHD) derivatives, as disclosed in GB-A-907,356, GB-A-907,357 and GB-A-907,358;
d) Acylated glycolurils, such as tetraacetylglycoluril, as disclosed in GB-A-1,246,338, GB-A-1,246,339 and GB-A-1,247,429.

2) Acylated sulphon~mi~les, such as N-methyl-N-benzoyl-menthane sulphon~mifle and N-phenyl-N-acetyl menth~ne sulphon~mitle, as disclosed in GB-A-3,183,266.

3) Carbo~cylic esters as disclosed in GB-A-836,988, GB-A-963,13 and GB-A-1,147,871. E~camples of compounds of this type include phenyl ~ce~te, sodium aceto~cy benzene sulphonate, trichloroethylacetate, sorbitol he~caacetate, fructose pentaacetate, p-nitroben~lf1ehyde ~ cet~te~ isopropeneyl ~cet~te, acetyl aceto hydro~camic acid, and acetyl salicylic acid. Other e~camples are esters of a phenol or substit~-te~l phenol with an alpha-chlorinated lower aliphatic carbo~ylic acid, such as chloroacetylphenol and chloroacetylsalicylic acid, as disclosed in US-A-3,130,165.

4) Carbo~ylic esters having the gernal formal Ac L wherein Ac is the acyl moiety of an organic carbo~cylic acid comprising an optionally sub~ ul~l, linear or branched C6-C20 alkyl or alkenyl moiety or a C6-C20 alkyl-substit~te~l aryl moiety and L
is a leaving group, the conjugate acid of which has a pKa in the range from 4 to 13, for e~cample o~cybe~7Pnesulfonate or o~rl,c,~oate. P~efelled compounds of this type are those wherein:
a) Ac is R3-CO and R3 is a linear or branched alkyl group cont~inin~ from 6 to 20, prefelably 6 to 12, more ,refelably 7 to 9 carbon atoms and wherein the longest linear alkyl chain e~ctending from and including the w o96rl9s61 P ~ ~US95~1667Z

carbonyl carbon contains from ~ to 18, preferably 5 to 10 carbon atoms, R3 optionally being substi~e~l (preferably alpha to the carbonyl moiety) by Cl, Br, OCH3 or OC2Hs.
E~amples of this class of material include sodium 3,5,5-trimethylhe~canoylo~ybenzene sulfonate, sodium 3,5,5-trimethylhe~anoylo~ybenzoate, sodium 2-ethylhe~anoyl o~cybenzenesulfonate, sodium nonanoyl o~cybenzene sulfonate and sodium octanoyl o~cybenezenesulfonate, the acylo~y group in each instance ~ref~rably being p-substi~ltetl;

Ac has the formula R3(AO)mXA wherein R3 is a linear or branched alkyl or alkylaryl group cont~inin~ from 6 to 20, ~rerel~bly from 6 to 15 carbon atoms in the alkyl moiety, Rs being optionally substit~te~l by Cl, Br, OCH3, or OC2Hs, AO is o~cyethylene or o~ypropylene, m is from O
to 100, X is 0, NR4 or CO-NR4, and A is CO, CO-CO, R6-CO, CO-R6-CO, or CO-NR4-R6-CO wherein R4 is Cl-C4 alkyl and R6 is alkylene, alkenylene, arylene or alkarylene cont~inins~ from 1 to 8 carbon atoms in the alkylene or alkenylene moiety. Bleach activator compounds of this type include carbonic acid deliva~ives of the formula R3(AO)mOCOL, succinic acid derivatives of the formula R30CO(CH2)2COL, glycollic acid derivatives of the formula R30CH2COL, hydro~cypropionic acid derivatives of the formula R30CH2CH2COL, o~calic acid derivatives of the formula R30COCOL, maleic and fumaric acid de~ivalives of the formula R30COCH=CHCOL, acyl ~minoc~l)roic acid derivalives of the formula R3CONR1(CH2)6COL, acyl glycine delivalives of the formula R3CONRlCH2COL, and amino-~o~cocaproic acid de.iv~lives of the formula R3N(R1)CO(CH2)4COL. In the above, m is preferably from O to 10, and R3 is l,refeiably C6-C12, more prefelably C6-Clo aLkyl when m is zero and Cg-C1s when m is non-zero. The leaving group L is as defined above.

W O9G/19S61 PCTnUS9S/16672

5) Acyl-cyanurates, such as triacetyl- or tribenzoylcyanurates, as disclosed in US patent specification No. 3,332,882.

6) Optionally substituted anhydrides of benzoic or phthalic acid, for e~ample, 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 caprol~t~m and their substituted benzoyl analogs such as the chloro, amino, alkyl, aryl and alko~cy derivatives.

Of all the above, ~refe~red are organic peracid precursors of types 1 (c), 4(a) and 7.

Where present, the level of pero~cyacid 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 ~referred for use herein generally comprise a binder or agglomerating agent in a level of from about 5 %
to about 40%, more especially from about 10% to about 30% by weight thereof. Suitable agglomerating agents include polyvirlylpyrrolidone, poly (o~cyethylene) of molecular weight 20,000 to 50(),000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowa~c having a molecular weight of from 4000 to 20,000, nonionic surf~rt~nt~, fatty acids, sodium carbo~ymethyl cellulose, gelatin, fatty alcohols, phosphates and polyphosphates, clays, ~ minosilicates and polymeric polycarbo~ylates. Of the above, polyethyleneglycols are highly ;fel r~d, especially those having molecular weight of from about 1,000 to about 30,000, prererably 2000 to about 10,000.

rlefe~ d from the viewpoint of o~limum dissolution and pH
characteristics are bleach precursor agglomerates which comprise from W O96/19S61 PCTnUS9Sn6672 about 10% to about 75%, preferably from about 20% to about 60% by weight thereof of pero~cyacid bleach precursor, from about S ~o to about 60% ~lefe~ably from about ~% 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 pero~coboroate, 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, ~referably ~rom about 500 to a~out 1,000 um, this being valuable from the viewpoint of optimum dissolution pelr~ llllance and aesthetics. The level of bleach precursor agglomerates, moreover, is preferably from about 1% to about 20%, more yrefelably from about 5% to about 15%
by weight of composition.

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

Bleaching compositions of the invention can be supplemented by other usual components of such formulations, especially surf~cPntc as generally described above, chelating agents, enzymes, dyestuffs, sweeteners, tablet binders and fillers, foam depress~nt~ such as tlimetllylpolysilo~anes, ~oam stabilizers such as the l~atty acid sugar esters, preservatives, lubricants such as talc, m~nesium stearate, finely divided amorphous pyrogenic silicas, etc.

Tablet binders and fillers suitable for use herein include polyvinylpyrrolidone, poly (o~cyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowa~c having a molecular weight of from 4000 to 20,000, nonionic surf~ct~ntc, fatty acids, sodium carbo~cymethyl cellulose, gelatin, fatty alcohols, clays, polymeric polycarbo~cylates, sodium carbollate, calcium carbonate, calcium hydro~cide, m~n~sil-m o~cide, m~nesillm hydro~ide carbonate, sodium slllf~te, l,ro~eills, cellulose ethers, cellulose esters, polyvinyl alcohol, alginic acid esters, vegetable fatty matelials of a pseudocolloidal character. Of the above, polyethyleneglycols are highly ~r~felled, W O96/19S61 PCTrUS9S/16672 especially those having molecular weight of from about 1,000 to about 30,ûO0, preferably from about 12,000 to about 30,000.

Chelating agents beneficially aid cleaning and bleach stability by keeping metal ions, such as calcium, m~nesium, and heavy metal cations in solution. E~camples of suitable chelating agents include sodium tripolyphosphate, sodium acid pyrophosphate, tetrasodium pyrophosphate, aminopolycarbo~cylates such as nitrilotriacetic acid and ethylene.li~min~ tetracetic acid and salts thereof, ethylen~ mine-N,N'-disuccinic acid (EDDS) and salts thereof, and polyphosphonates and ~minopolyphosphonates such as hy~ro~cyeth~ne-lirhosphonic acid, ethylen~i~min~ tetramethylenephosphonic acid, diethylenetri~minepent~methylenephosphonic acid and salts thereof.
The chelating agent selected is not critical e~cept that it must be c~ t;hle with the other ingredients of the denture cleanser when in the dry state and in aqueous solution. Advantageously, the chelating agent comprises between 0.1 and 60 percent by weight of the composition and ~refe~ably between 0.5 and 30 percent. Phosphonic acid chelating agents, however, ~le~rably comprise from about 0.1 to about 1 percent, ~fefelably from about 0.1 % to about 0.5 ~ by weight of composition.

Enzymes suitable for use herein are e~emplified by proteases, k~l~ees, amylases, fungal and bacterial lipases, de~ctranases, ",l~t~ ces, ~lllc~n~ees, esterases, cellulases, pectin~e-es~ lactases and pero~ ees, etc. Suitable enzymes are ~liec~leee~l in US-A-3,519,570 and US-A-3,533,139.

The following E~camples further describe and demonstrate the ~lefir~ed embo~liment~e within the scope of the present invention.

wo s6rlss61 P~-l~U~,S/16672 FXAMPLES I TO V

The following are representalive denture cle~n.~in~ tablets according to the invention. The percentages are by weight of the total tablet. The tablets are made by compressing a mi~cture of the gr~n~ te~
components in a punch and dye tabletting press at a pressure of about 105 kPa.

II III IV V
Malic Acid 12 10 15 - 14 Citric Acid - 10 - 15 Sodium Carbonate 10 8 10 6 10 Sulphamic Acid 5 - 3 3 PEG 20,000 - 3 7 8 5 PVP 40,000 6 3 Sodium Bicarbonate 23 24 25 23 24 Sodium Perborate Monohydrate 15 12 16 30 15 Pot~sium Monopersulphate 15 18 13 - 14 Pyrogenic Silica - 3 Talc 2 - - - -EDTMPl FlavorS 2 1 2 1 2 Abil EM9o4 1 1.5 0.5 2 Bleach Precursor Agglomerate 9 8 10 12 10 Rleach Precursor A~lomerate I II m IV v TAED2 2 - 4 5 2.5 TMHoS3 2 3 Sulphamic Acid 2 2 2 2 3.5 SodiumBicarbonate 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. EthylenP,rli~min~tel~...elllylenephosphonic acid 2. Tetraacetylethylene ~ mine 3. So~il)m 3,5,5-trimethylhe~canoylo~cybenzene sulfonate 4. Cetyl fiimP~thicone copolyol W O96/19S61 PCTnUS95/16672 5 Peppermint-based flavor In Examples I to V above, the overall tablet weight is 3 g; diameter 25 mm.

The denture cle~n~in~ tablets of E~camples I to V display improved antiplaque,cle~n~in~ and anti-bacterial activity together with e~cellent 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 perce:ntages are by weight of total composition.

VI VII VIII IX

PPG- 5-ceteth-20 3 .0 3 .0 4.5 3 .0 PEG40 hydrogenated castor - 1.8 4.5 3.0 oil Tri(lecetll-12 2.0 Tri~leceth-9 - 2.0 - 3.0 FlavorS 2.0 3.0 Perfilme6 - 3.0 Trimethyl l,~ e 0.3 0.5 Triclosan - - 1.0 0.5 Abil EM904 1.0 1.5 5.0 1.0 Water < - --- - ---- to 100% - - - ---- >

6. Perfume is a comple~c mi~cture of ingre~lient~ used ~.hllarily for olfactory purposes.

The ~elrume, flavor, coolant and/or antimicrobial compositions of F~ nples VI to IX display improved surface-subsl~tivily, impact and/or efficacy.

Claims

1. A bleach composition comprising an inorganic persalt bleaching agent, a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof, and a dimethicone copolyol selected from alkyl- and alkoxy-dimethicone copolyols having the formula (I):

wherein X is selected from hydrogen, alkyl, alkoxy and acyl groups having from about 1 to about 16 carbon atoms, Y is selected from alkyl and alkoxy groups having from about 8 to about 22 carbon atoms, n is from about 0 to about 200, m is from about 1 to about 40, q is from about 1 to about 100, the molecular weight of the residue (C2H4O-)x(C3H6O-)yX is from about 50 to about 2000, and x and y are such that the weight ratio of oxyethylene:oxypropylene is from about 100:0 to about 0:100.

2. A composition according to Claim 1 wherein the dimethicone copolyol is selected from C12 to C20 alkyl dimethicone copolyols and mixtures thereof.

3. A composition according to Claim 1 or 2 wherein the dimethicone copolyol is cetyl dimethicone copolyol.

4. A composition according to any of Claims 1 to 3 comprising from about 0.01% to about 25%, preferably from about 0.1% to about 5% by weight of the dimethicone copolyol.

5. A composition according to any of Claims 1 to 4 wherein the inorganic persalt bleaching agent comprises one or more bleaching agents selected from alkali metal persulfates, alkali metal perborates and mixtures thereof.

6. A composition according to any of Claims 1 to 5 wherein the flavorant comprises 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, marjoram oil, citronella oil, lavendar oil, mustard oil, pine oil, pine needle oil, rosemary oil, thyme oil, cinnamon leaf oil, and mixtures thereof.

7. A composition according to any of Claims 1 to 6 wherein the perfume comprises one or more perfume components selected from geranyl acetate, linalyl acetate, citronellyl acetate, dihydromyrcenyl acetate, terpinyl acetate, tricyclodecenyl acetate, tricyclodecenyl propionate, 2-phenylethyl acetate, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate, methyl dihydrojasmonate, phenoxyethyl isobutyrate, neryl acetate, trichloromethyl-phenylcarbinyl acetate, p-tertiary butyl-cyclohexyl acetate, isononyl acetate, cedryl acetate, vetiveryl acetate, benzyl alcohol, 2-phenylethanol, linalool, tetrahydrolinalool, citronellol, dimethylbenzylcarbinol, 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-amylcinnamic aldehyde, alpha-hexyl-cinnamic aldehyde, 4-(4hydroxy-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, geranonitrile, citronellonitrile, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropine, coumarin, vanillin, diphenyl oxide, ionones, methyl ionones, isomethyl ionones, irones, cis-3-hexenol and esters thereof, indane musks, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brassylate, aromatic nitromusks and mixtures thereof.

8. A composition according to any of Claims 1 to 7 additionally comprising an effervescence generator.

9. A composition according to any of Claims 1 to 8 additionally comprising an organic peroxyacid bleach precursor.

10. A composition according to Claim 9 wherein the organic peroxyacid bleach precursor is selected from acylated polyalkyldiamines, especially tetraacetylethylenediamine, and carboxylic esters having the general formula AcL wherein Ac is the acyl moiety or an organic carboxylic acid comprising an optionally substituted, linear or branched C6-C20 alkyl or alkenyl moiety or a C6-C20 alkyl-substituted aryl moiety and L
is a leaving group, the conjugate acid of which has a pKa in the range from 4 to 13.

11. Use of a dimethicone copolyol with an inorganic persalt bleaching agent and a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof to provide improved lipophile stability, wherein the dimethicone copolyol is selected from alkyl- and alkoxy-dimethicone copolyols having the formula (I):