CA2208462A1 - Silicone compositions - Google Patents

Abstract

A bleach composition comprising an inorganic persalt bleaching agent, a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof, and an aminoalkylsilicone having an aminoalkylsiloxane content of from about 0.1 % - 2 % on a repeating unit basis. The composition provides improved lipophile and bleach stability.

Description

2 . PCT/US9511576S

SILICONE COMPOSlTIONS

TECHNICAL FIELD

The present invention relates to silicone-con~ining compositions and to use thereof in various household products such as personal care products, laundry and household cleaners, bleaching compositions and the like. In particular, it relates to silicone-cont~ininE lipophilic compositions based on flavorants, pelrunles, coolants or antimicrobial agents as lipophile and which display improved residn~lity, imr~ct 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-cont~inin~ bleach compositions which ~d~itionally contain bleach-sensitive ingredients such as pel~mes, flavorants and the like and which display imp,oved stability.

BACKGRQUND

Lipophilic compositions such as flavor, l,e~rume, coolant and disinfectant compositions are widely used either directly or in a variety of household products inclusive of cosmetics~ oral and denlure compositions, bleach, dishw~shing, hard surface cle~ning and laundry delelgc;nt products, etc.
A common problem enc~untered with lipophilic compositions is that of improving surface sub~livil~r or resi~ lity of the lipophilic component.
It would be desirable in many if not most household applications to enh~nce the surface resi~ lity of the lipophile in order, for example, to provide iuc~eased 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 flavol~. Antimicrobial action could affect plaque formation by either reducing the mlmber of bacteria in the mouth/delllures or by killing those bacteria llapped 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 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 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 ~ntimicrobial agents in the ~repalations to take effect. The problem is compounded by the fact that ~i~ntifrice preparations are used infrequently; most are used once or, ,elLaps, twice daily. Consequently, the long time period between brll~hin~c for a majority of the population provides opt;....~ plaque îo~uung conditions.

In many other personal and household applications, it would be desirable to provide enh~nce~ surface sub~ ivily. ~ n~ry deler~nts, for e~mrle, would benefit by increasing l,elruule subs~ntivily on fabrics so as to provide increased pelruule imp~ct on clothing after l~nn~lering or rin~ use. Increased ~ntimicrobial sul,s~livily would also be beneficial from the viewpoint of reducing malodors associated with sweat or other soils. Fnh~nce l perfume subs~nlivily would also be valuable in fine fragrance and pelruuued cosmetics. Pnh~nce~l coolant sllbs~ ;vily, on the other hand, would be beneficial in cough/cold products.

There has been a need, thererolG, for developing lipophilic compositions which have h~ oved surface residu~lity, imp~ct and/or antimicrobial efficacy.

The use of lipophilic compounds such as pe.rumes, flavorants and the like in bleachcont~inin~ coul~osilions can also raise a number of problems, especially loss of l,clruule or flavorant character or inten~ity as a result of interaction with the bleach. The efficacy of the blç~c-hin~ agent can also be adversely effecte~l. It would thus be desirable to i,llprove the stability and effectiveness of bleach compositions cont~iniT~ bleachsensitive ingredients.

-It is known to include silicones in ~l~ntifrice compositions, allegedly to coat the teeth and prevent cavities and st~inin~. For inctance, GB-A-689,679 discloses a mouthwash cont~ining an organopolysiloxane for ~reventillg adhesion of, or for removing tars, stains, 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 amino 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, stains, tartar and the like from teeth. The silicone col~oulld is said to act as a synergist in improving the ~ntib~cterial and acid inhibiting activity of the active ingre~lient. Dilllc~yl polysiloxanes are said to be particularly erre-;live. Flavoring oils and/or m~nthol may be included.

US-A-3624120 discloses quatel~aly ammonium salts of cyclic siloxane polymers for use as cationic surfact~nts, bactericides and as antiC~riogeniC agents.

Accor~ gly, the present invention provides a flavor, pelr~ le, coolant, antimicrobial or other lipophilic composition having improved surface-s~ll)s~ t;vily, jmp~ct and/or efficacy.

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

SUMMARY OF T~F INVFNTION

~ Acco~i~g to a first aspect of the invention, there is provided a flavor, pc~runle, coolant, antimicrobial or other lipophilic composition co~ ising an ~mino~ ylsilicone having an ~mino~lkylsilo~cane content of from about 0.1%-2% on a repe~tin~ unit basis.

WO 96/19562 . PCT/US95/15765 The invention also relates to the use of an aminoalkylsilicone with a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mi~lres thereof to provide i...~.o~ed surface resi~ lity, wherein the ~mino~lkylsilicone is selected from ~mino~lkylsilicones having an ~mino~lkylsilo~cane content of from about 0.1%-2% on a repe~tin~ unit basis.

According to a further aspect of the invention, there is provided a bleach composition co..lp.ising an inorganic persalt ble~chin~ agent, a lipophile selected from flavorants, pe-ru.lles, physiological coolants, ~ntimicrobial agents and mixtures thereof, and an ~mino~lkylsilicone having an ~mino~lkylsilo~cane content of from about 0.1%-2% on a repe~tin~ unit basis.

The invention also relates to the use of an ~mino~lkylsilicone with an inorganic persalt ble~chin~ agent and a lipophile selecteA from flavorants, perfumes, physiological coolants, ~ntimicrobial agents and mi~hlres thereof to provide i.~roved lipophile stability, wherein the ~mino~lkylsilicone is selected from ~mino~lkylsilicones having an ~mino~lkylsilo~cane content of from about 0.1%-2% on a repeating unit basis.

All ~erce~ ges and ratios herein are by weight of total composition, unless otherwise in~ic~te~l The co~osilions of the invention thus comp-ise an ~mino~lkylsilicone antiplaque agent and a lipophile sclcctel from flavorants, perfumes, physiological coolants, antimicrobial agents and m~ res thereof. Other compositions of the invention take the form of bleach and/or delel~ent compositions which co~l,.ise the ~mino~lkylsilicone antiplaque agent and lipophile.

In general terms, the ~mino~lkylsilicone is selected from noncyclic, hydrophobic ~mino~lkysilicones having a formula co-nprising two basic units:

WO 96/19562 . PCT/US95/15765 1) (Rl)m(R)nSiO(~m n)/2 wherein m+n is 1, 2 or 3; n is 1, 2 or 3;
m is 0,1,2; and 2) (R1)a(R2)bSio(~a-b)/2 wherein a+b is 1, 2, or 3, and a and b are integers, wherein Rl and R2 are indepen~e.lltly selected from H ,alkyl and alkenyl of about 1 to about 10 carbons optionally subs~ ~l with fluoro or cyano groups, hydro~cy, alkoxy, and acetoxy, for e~cample, wherein Rl and R2 are indepen~l~ntly selected from methyl, ethyl, phenyl, vinyl, trifluor~pro~yl and cyanopropyl, and R is --R3--N-R5 or --R3--N-R5 X

wherein R3 is a divalent alkylene of about 1-20, ~reîerably about 3-5 carbon atoms optionally sul,~ .te~ or mte~lu~led by O atoms, R4, R5 and R6 which may be the same or dirrelent are selected from H, alkyl of about 1-20, l,~ere~dbly about 1-10, more l,rcfelably about 14 carbons optionally sul,s~ le~ or intellu~ted by N and/or O atoms, and X~ is a monovalent anion such as halide, hydro~cide, and tosylate, said aminoalkylsilicone including from about 0.1-2 %, yrererably from about 0.5-2% of unit (1) on a repe~tin~ unit basis.

In a ~lere~ embo~ ent, the ~mino~lkylsilicones comprise ~moAimethicones. ~mo.limethicones are poly~limPthylsilo~ane polymers co~ mino~llryl groups. The ~mino~lkyl ~r~,~s may be present either pen~l~nt or at one or more ends of the poly limetllylsiloxane chain.
Pr~felr~d are ~mino~lkylsilicones in which ~mino~lkyl moiety R is selected from (cH2)3NH2~ (cH2)3NHcH2cH2NH2 (CH2)3N(CH2CH2OH)2, (CH2)3NH3+X-, and (CH2)3N(CH3)2(C18H37)+X-, and especially from (CH2)3NH2 and (CH2)3NHCH2CH2NH2. Also p.er~ed are aminoalkyl silicones having an average molecnl~r weight of about S,000 and above, preferably from about 5000 to about 100,000, more plel~lably from about S000 to about 30,00~.

WO 96/19562 . PCT/US95/1~765 ,AminQ~lkylsilicone compounds suitable for use herein are well known.
Methods of preparing ~mino~lkylsilicones are given in, for example, US-A-2,930,809.

F.~mpleS of amo~limethicones include OSI's M~n~oft fluid. These polymers colllprise ~min~llcyl groups :lfflXe~ to a predo--~inA.~tly poly~limethylsiloxane structure. The typical structure of ~n~oft's ~mino~llryl group-cont~inin~ units is -OSi(Me)C3H6NHCH2CH2NH2.

The ~mino~ ylsilicone is generally present in a level of from about 0.01% to about 25 % , p~ere~ably from about 0. 1% to about 5 %, more prefelably from about 0.5% to about 1.5% by weight.

The compositions of the invention prefe~dbly also include a lipophilic compound. In general terms, lipophilic compounds suitable for use herein are oil-like materials which are soluble or solubilisable in the ~min~ ylsilicone, prerel~bly at a level of at least about 1%, more ~rererably at least about 5% by weight at 25~C. rrerelled lipophilic compounds are selected from flavorants, perfumes, physiological cooling agents and ~ntimicrobial compounds. The aminoalkylsilicone acts to enh~nGe the snbsl~t;vily of the lipophilic compound to a surface treated there~vi~, thereby providing enh~nce~ and/or sllst~in~A flavor, perfume or coolant imr~ct and/or antimicrobial efficacy.

Lipophilic flavorants suitable for use herein comp~ise one or more flavor colll~one.~ls selected from willtergreen oil, olcgallo oil, bay leaf oil, ~ int oil, s~ealll~i~t oil, clove oil, sage oil, s~ss~fras oil, lemon oil, orange oil, anise oil, ben7~ldehyde, bitter almond oil, camphor, cedar leaf oil, marjoram oil, citronella oil, lavendar oil, mns~rd oil, pine oil, pine nee~le oil, rosemary oil, thyme oil, cinn~mQn leaf oil, and mi~ctures thereof.

Lipophilic ~lrumes suitable for use herein comprise one or more known pelrullle com~ollents inclusive of natural products such as essenti~l oils, absolutes, resins, etc., and synthetic perfume components such as =

WO 96/19562 . PCTIUS95115765 hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acet~
ketals, nitriles etc., including saturated and llne~tllrated compounds, aliphatic, carboxylic and heterocyclic compounds. F.x~mples of perfume materials suitable for use herein include geranyl ~cet~te, linalyl acetate, citronellyl ~cet~te, dihydromyrcenyl ~cet~te, terpinyl ~cet~te, tricyclo~lecenyl ~cet~te, tricyclodecenyl propionate, 2-phenylethyl ~cet~te, benzyl ~cet~te, benzyl salicylate, benzyl ben~o~te, styrallyl ~cePte, amyl salicylate, methyl dihydrojasmonate, phenoxyethyl isobulylate~ neryl ~cet~te, trichloromethyl-phenylcarbinyl ~cePte, p-tertiary butyl-cyclohe~yl ~cet~te, isononyl ~cet~te, cedryl ~cet~te, vetiveryl ~cet~te, benzyl alcohol, 2-phenyleth~nol, linalool, tetrahydrolinalool, citronellol, ~limethylbenzylcarbinol, dihydromyrcenol, tetrahydromyrcenol, terpineol, eugenol, geraniol, vetiverol, 3-isocamphyl-cyclohexanol, 2-methyl-3-(p-tertiary butylphenyl)-propanol, 2-methyl-3-(p-isopropylphenyl)-~ropanol, 3-(p-tertiary butylphenyl)-yrop~ol, nerol, alpha-n-amylcinn~mic aldehyde, alpha-he~cyl-cinn~mic aldehyde, ~(~hydroxy~methylpentyl)-3-cyclohP~enec~rb~l~lehyde, ~(~methyl-3-pentenyl)-3-cyclohe~enec~rb~l~lehyde, ~acetoxy-3-pentyl-tetrahydropyran, 2-n-heptyl-cyclopçnt~none, 3-methyl-2-pentyl-cyclopent~nQne, n~lec~n~l, n-~lo~ec~n~l, hydroxycitronellal, phenyl~cet~ldehyde ~lim~thyl ~cet~l, phenyl~c~al~lehyde diethyl acet~l, ger~nonitrile, citronellonitrile, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliolropille, CO.llllalln, v~nillin, ~lirh~nyl oxide, ion~.ne~, methyl ionones, isomethyl ionones, irones, cis-3-h~x~n~l and esters thereof, ind~ne musks, tetralin musks, isochro~n musks, macrocyclic ketones, macrol~ctone musks, ethylene brassylate, aromatic nillol,lusks and mi~ res thereof.

Lipophilic antimicrobial compounds suitable for use herein include thymol, m.o.nth~l, triclosan, ~hexylresorcinol, phenol, eucalyptol, benzoic acid, be~oyl peroxide, butyl paraben, methyl paraben, propyl paraben, salicyl~mides, and n~ res thereof.
~.~
Physiological cooling agent suitable for use herein inclllde carbo~amides, m~ ..e esters and mrn~ . ethers, and mixtures thereof.

Suitable n~ n1l.~ne ethers for use herein are selected from those with the formula:

WO96119562 . Pcr/uS95/15765 OR~

where Rs is an optionally hydro~y substi~lteA aliphatic radical cont~ining up to 25 carbon atoms, ~rere~ably up to 5 carbon atoms, and where X is hydrogen or hydro~cy, such as those commercially available under the trade nameT~ o, fromT~ o Inle~llational Corporation. A
particularly l,rerelled cooling agent for use in the compositions of the presenl invention is T~k~ o 10 [3~ .o~cy pr~pan-1,2-diol (MPD)].
MPD is a monoglycelin delivalive of l-m~.ntllrll and has e~cellent cooling activity.

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

The level of lipophilic com~G.~nd in the con~osilions of the invention is generally in the range from about 0.01% to about 10%, ~referably from about 0.05% to about 5%, more ~refelably from about 0.1% to about 3%
by weight.

The co~l~osil;ons of the invention optionally include one or more surf~ct~n~, these being especially prefe~d in lipophilic compositions of the illvention for the ~ ,ose of solubili7~tio~ of the lipophile and for providing illl~JrOVed efficacy. Suitable surf~ct~nt~ include non-soap anionic, nonionic, cationic, ;~willerionic and amphoteric organic synthetic delelge~ . Many of these suitable agents are disclosed by Gieske et al. ~-in US-A-4,051,234, Se~tember 27, 1977.

F.~mrles of surf~ct~nts suitable for use herein include C6-Clg alkyl s~llf~tes and alkyl ether s~llf~tes etho~cylated with from about 0.5 to about 20 moles of ethylene o~cide per mole; anionic sulro-~ates inclusive of Cs-W O96/19562 PCTrUS95/15765 C20 linear alkylben7ene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, and mixtures thereof; anionic carboxylates inclusive of primary and secondary C6 to Clg alkyl carboxylate, ethoxy carboxylate and polyetho~cy polycarboxylate surf~ct~nts having an average degree of ethoxylation of from about 0 to about 10; Cs-C17 sarcosm~tes such as sodium cocoylsarcosinate, sodium lauroyl sarcosinate (Hamposyl-95 e~c W. R. Grace); con~1en~tion products of ethylene or pro~ylene oxide with fatty acids, fatty alcohols, fatty ~mirles, polyhydric alcohols (e.g. sorbitan monostearate, sorbitan oleate), alkyl phenols (e.g. Tergitol) and polypropyleneoxide or polyo~cybutylene (e.g. Pluronics);
alkylpolys~cch~rides as disclosed in US-A ~1,565,647; amine oxides such as ~1imetllyl coc~mine oxide, t1imetllyl lauryl amine o~cide and cocoalkylllimet!~yl amine oxide (Aromox); polysorbates such as Tween 40 and Tween 80 (Hercules); sorbitan stearates, so~ dll monooleate, etc;
cationic surf~ct~nts such as cetyl pyri~linil.m chloride, cetyl trimethyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl-dimethyl benzyl ammonium chloride and coconut alkyl trimethyl ammonium nitrate.

Highly prefclr~l herein from the view point of lipophile solubilization are the nonionic surf~ct~ntc. One class of nonionic surf~cPnt suitable for use herein are those having the general formula:

Rl--(OCHCH2)m (OCH2CH2) n OH

in which Rl is an alk(en)yl or alk(en)yl phenyl group having 8 to 22, prefe~dbly 10 to 20 carbon atoms ion the aLk(en)yl moiety and m and n r~resent weight-averages in the range 0-80 and 2-80 respectively.
Shorter chain length alkyl grou~s are generally to be avoided for efficacy re~on.c and bec~se unreacted fatty alcohol in such surf~ct~nts is a source of malodour and occasionally of skin irritation. It will be understood that surf~ct~nts of this type are usually mixtures of varying degrees of etho~cylation / propoxylation, accordingly m and n represent the respective weight-averages of the number of propoxylate and ethoxylate WO 96/19562 PCrlUS95115765 groups. Nonionic surfact~nt~ of the above general type include mixed alkoxylates in which m and n are both in the range from about 2 to about 80, with m preferably being in the range from about 2 to about 20, more prererably from about 3 to about 10 and with n preferably being in the range from about 2 to about 60, more preferdbly from about 5 to about 50. One such malerial is PPG-5-ceteth-20 (available from Croda Inc as Procetyl AWS), where m and n have the values 5 and 20 respectively.
Other suitable nonionic surf~ctant~ include polyetho~ylated surf~ctants, e.g. etho~cylated alkylphenol ethers, particularly octyl- and nonylphenol ethers cont~inin~ 8-16 EO; ethoxylated aliphatic Cg-C20 alcohols, which may be linear or branched and contain 8-16, pleferably 9-15 EO; and ethoxylated hydrogenated castor oils.

In general, the ratio of surf~ct~nt to the pelrullle, coolant or other oily material will be in the range of from about 50:1 to about 1:10, prefe~ably from about 20:1 to about 1:2, more prere~ably from about 10:1 to about 1:1.

Ble~c.hing compositions of the invention additionally include one or more ble~c.hing agents optionally together with organic pero~cyacid precursors, err~ escence generatol~, chelating agents, etc The ble~c.hing agent takes the form of an inorganic persalt and can be selected from any of the well-known ble~chin~ agents known for use in household ble~c.hes, dele~en~, delllurG clç~n.cers and the like such as the alk~ali metal and ammonium perslllf~tes, perborates inclusive of mono-and tetrahy~lates~ ~ere~lbonates (optionally coated as described in GB-A-1,466,799) and perphosph~tes and the alkali metal and ~lk~lin~ earth metal pero~cides. F.~mples of suitable ble~chin~ agents include po~.csjllm~ ammonium, sodium and lithillm perslllf~te~ and perborate mono- and tetrahydrates, sodium pyrophosphate pero~cyhydrate and m?~pnesjllm, calcium, strontium and zinc pero~cides. Of these, however, the alkali metal perslllf~tes, perborates, percarbonates and nnixtures thereof are l.rere-ed for use herein, highly p~erer,ed being the alkali metal perborates and percarbonates.

W O 96/19562 . PCTrUS95tl5765 The amount of ble~ching agent in the bleaching compositions of the invention is generally from about S to about 70% preferably from about 10% to about 50%.

The ble~chin~ compositions can also incorporate an effervescence generator which in prc;rer~ed embo~iment~s 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 generatoLs which are effective under acid, neutral or ~lk~linP pH
conditions, but ~lefelably 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 ~ line pH
conditions. EffervescenGe generators which are effective under acid or neutral pH conditions include a combination of at least one alkali metal carbonate or bicall,onate, such as sodium bicarbonate, sodium carbonate, soAillm sesquicarbonate, pot~sium carbonate, pot~ssillm bicarbonate, or mi~tures thereof, in ~rimi~ re 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 fumarate, sodium or potassium acid phosphates, betaine hydrochloride or mi~ctures thereof. Of these, malic acid is ~refe~cd.
EffervescenGe generators which are erreclive under ~ line pH conditions include persalts such as alkali and ~ line earth metal peroxoborates as well as ~cl~orates~ pers~llph~tes, percarbonates, perphosphates and mi~ res thereof as previously described, for e~ample, a mixture of an alkali metal perborate (anhydrous, mono- or tetrahydrate) with a mono~el~.Jlrh~te such as Caroat R marketed by E I du Point de Nemours Co. and which is a 2:1:1 mi~tllre of monopcl~vlrh~te, pot~csillm sulphate and pot~c~sillm bisulphate and which has an active o~cygen colltent of about 4.5%.

In ~refelr~d 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 ~timum dissolution characteristics and pH conditions for achieving ~limum clç~nin~ and antimicrobial activity. The (bi)carbonate W O96/19562 PCTnUS9~/1576 components generally coll,ylise from about S~ to about 65%, preferably from about 25 % to 55% of the total composition; the acid components generally colll~iise from about S % to about 50%, preferably from about 10% to about 30% of the total composition.

The ble~hin~ compositions of the invention can be supplemented by other known compollents of such form~ tions. An especially preferred additional component is an organic pero~yacid 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.

A test solution is pr~ared by dissolving the following materials in 1000 mls ~iictille~ water:

sodium pyrophosphate (Na4P2O7- l~H2~) 2.5g so~ m pell,o~ate (NaBO2.H2O2.3H2O) having 10.4% available o~cygen 0.615g sorlillm dodecylbe~
sulphonate O.Sg To this solution at 60~C an amount of activator is added such that for each atom of available o~cygen present one molecular equivalent of aclivat~r is intro~luGed.

The ~ vre obt~ine~ by ~d~lition of the activator is vigorously stirred and ",s~i"t~i~,e~ at 60~C. After S .~in~tes from addition, a 100 ml portion of the solution is wilhdla~n and imme~i~tely pipetted onto a mi~ture of 250 g cracked ice and 15 ml glacial acetic acid. PoPssi~lm iodide (0.4 g) is then added and the lil~eiated iodine is imm~li~tely titrated with 0.1 N
so~ m t~ios~11rhate with starch as in~lic~tQr until the first disappearance of the blue colour. The amount of sodium thioslllrh~te solution used in ml is the titre of the bleach activator.

The organic peracid ~rec.lrjors are typically compounds cont~ining one or more acyl groups, which are sllsceptible to perhydrolysis. The preferled W O96119562 PCTrUS95tl5765 activators are those of the N-acyl or O-acyl compound type cont~ining a acyl radical R-CO wherein R is a hydrocarbon or sul~sl;lule~l hydrocarbon group having plc~lably from about 1 to about 20 carbon atoms.
Examples of suitable peracid precursors include:

1) Acyl or~no~mi~es of the formula RCONRlR2, where RCO is carbo~cylic acyl radic~1, Rl is an acyl radical and R2 is an organic radical, as disclosed in US-A-3,117,148. Fs~mrles of compounds falling under this group include:

a) N,N - diacetyl~niline and N-acetylphth~limi~e;
b) N-acylhydanloins, such as N,N' -diacetyl-5,5~limethylhydantoin;
c) Polyacylated alkylene ~i~mines~ such as N,N,N'N' -tetraacetylethylen~i~mine (TAED) and the colle~onding he~methyleneAi~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 sulrhon~mi~les, such as N-methyl-N-benzoyl-m~nt~ne sulphon~mi~le and N-phenyl-N-acetyl nlPnth~ne sulphon~mi~le, as disclosed in GB-A-3,183,266.

3) Carbo~cylic esters as disclosed in GB-A-836,988, GB-A-963,135 and GB-A-1,147,871. F.~mrles of compounds of this type include phenyl ~Get~te, so~ m aceto~y l,e~ene sulphonate, trichloroethyl~cePte, sorbitol he~cet~te, fructose pent~cet~te, p-nilfol,c~ lehyde ~ cet~te, iso~ropcneyl ~cet~te, acetyl aceto hydro~amic acid, and acetyl salicylic acid. Other examples are esters of a phenol or subsl;~v~eA phenol with an alpha-chlorinated lower aliphatic carb~ylic acid, such as chloroacetylphenol and chloroacetylsalicylic acid, as disclosed in US-A-3,130,165.

4) Carbo~cylic esters having the gernal formal Ac L wherein Ac is the acyl moiety of an organic carbo~cylic acid comprising an optionally W O96/19562 PCTrUS95/15765 sul~sl;~u~ , linear or br~nche~l C6-C20 alkyl or alkenyl moiety or a C6-C20 alkyl-substit~lte~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 example oxybçn7enesl)lfonate or oxybenzoate. rrerel~ed compounds of this type are those wherein: ,~
a) Ac is R3-CO and R3 is a linear or br~nchPA alkyl group cont~ining from 6 to 20, l.refeiably 6 to 12, more ~rererdbly 7 to 9 carbon atoms and wherein the longest linear alkyl chain e~te.n~linP from and including the carbonyl carbon contains from S to 18, ~reftlably 5 to 10 carbon atoms, R3 optionally being substi~te~ )r~ Çelably alpha to the carbonyl moiety) by Cl, Br, OCH3 or OC2Hs. F.~mrles of this class of material include sodium 3,5,5-kimethylhe~noylo~cyben~en-P sulfonate, sot~ m 3,5,5-trimethylhexanoylo~cyl,c..~o~te, sodium 2-ethylhe~canoyl o~yl,e..~~~ Pslllfonate, sodium nonanoyl o~ybe..,e.~-~. sulfonate and sodium octanoyl o~cybenP~Pnesl)lfollate, the acyloxy group in each incpnce pre~e~ably being p-slll s~ e~l;

b) Ac has the formula R3(AO)mXA wherein R3 is a linear or br~n~h~l alkyl or alkylaryl group cont~ininp from 6 to 20, e~elably from 6 to 15 carbon atoms in the alkyl moiety, Rs being optionally sul,s~ leA by Cl, Br, OCH3, or OC2Hs, AO
is oxyethylene or o-~ypro~ylene, m is from 0 to 100, X is O, NR4 or CO-NR4, and A is CO, CO-CO, R6-CO, CO-R6-CO, or CO-NR4-R6-CO wherein R4 is Cl-4 alkyl and R6 is alkylene, alkenylene, arylene or alkarylene cont~ininp from 1 to 8 carbon atoms in the alkylene or alkenylene moiety.
Bleach activator compounds of this type include carbonic acid derivatives of the formula R3(AO)mOCOL, succinic acid de~ivalives of the formula R3OCO(CH2)2COL, glycollic acid derivatives of the formula R3OCH2COL, hydro~y~ropionic acid delivalives of the formula R30CH2CH2COL, o~calic acid delivatives of the formula R30COCOL, maleic and fumaric acid de~ivalives of the formula R30COCH=CHCOL,acyl aminocaproic acid derivatives of the formula R3CONRl(CH2)6COL, acyl glycine derivatives of the WO 96/19562 . PCT/US95tl5765 formula R3CONR1CH2COL, and amino-~oxocaproic acid derivatives of the formula R3N(R1)CO(CH2)4COL. In the above, m is preferably from 0 to 10, and R3 is prererably C6-C12, more ~refeiably C6-Clo alkyl when m is zero and Cg-C1s when m is non-zero. The leaving group L is as defined above.

S) Acyl-cya~ rates, such as triacetyl- or tribenzoylcyanurates, as disclosed in US patent specification No. 3,332,882.

6) Optionally substi~ute~ anhydrides of benzoic or phthalic acid, for e~cample, benzoic anhydride, m-chlorobenzoic anhydride and phthalic anhydride.

7) N-acylated precursor compounds of the l~ct~m class as disclosed generally in GB-A-855735, especially caprol~ct~m~ and valerol~ct~ms such as bc~oyl valerol~ct~m, benzoyl caprolactam and their Sl)bS~ Jle~ be~l:)yl analogs such as the chloro, amino, alkyl, aryl and alkoxy delivatives.

Of all the above, prefelled 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 prere.ably from about 0.1% to about 10%, more ere.~bly from about 0.5% to about 5% and is generally added in the form of a bleach prec.llsor agglomerate.

The bleach precursor agglomerates pfefclred for use herein generally coln~lise 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 polyvinyl~ylr()lidone, poly (o~cyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowax having a molecnl~r weight of from 4000 to 20,000, nonionic surf~ct~nt~, fatty acids, sodium carboxymethyl cellulose, gelatin, fatty alcohols, phosphates and polyphosphates, clays, ~ minosilicates and polymeric WO 96/19562 PCT/US95/1~765 polycarboxylates. Of the above, polyethyleneglycols are highly prefe~red, especially those having molecular weight of from about 1,000 to about 30,000, preferably 2000 to about 10,000.

rrefe~red from the viewpoint of op~ lum dissolution and pH
characteristics are bleach ~re~.lr~or agglomerates which collll,lise from about 10% to about 75%, pieferably from about 20% to about 60% by weight thereof of peroxyacid bleach precu.sor, from about 5% to about 60% prcfeldbly 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 pero~coboroate, and from about 5% to about 40%, ~referably 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 S00 to about 1,000 um, this being valuable from the viewpoint of optimllm dissolution yelror~ nce and ~sthetics. The level of bleach precursor agglomerates, moreover, is pre~lably from about 1% to about 20%, more prefe~dbly from about 5% to about 15% by weight of composition.

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

Ble~chin~ compositions of the invention can be supplement~l by other usual components of such formulations, especially surf~ct~nt~ as generally described above, ch~l~ti~ agents, enzymes, dyes(iJrr~ sweeteners, tablet binders and fillers, foam depress~nts such as ~limell~ylpolysiloxanes~ foam stabilizers such as the fatty acid sugar esters, preservatives, lubricants such as talc, m~gnps;ulll stearate, finely divided amorphous pyrogenic silicas, etc.

Tablet binders and fillers suitable for use herein include poly~inyl~y~lolidone, poly (o~cyethylene) of molecul~- weight 20,000 to 500,000, polyethyleneglycols of molec~ r weight of from about 1000 to about 50,000, Carbowax having a molecul~- weight of from 4000 to 20,000, nonionic surf~ct~nts, fatty acids, sodium carboxymethyl cellulose, g~l~tin, fatty alcohols, clays, polymeric polycarbo~cylates, sodium -WO 96J19562 . PCT/US95/15765 carbonate, calcium carbonate, calcium hydroxide, magnesillm oxide, m~ne.sium hydroxide carbonate, sodium s~llf~te, proteins, cellulose ethers, cellulose esters, polyvinyl alcohol, alginic acid esters, vegetable fatty materials of a pseudocolloidal character. Of the above, polyethyleneglycols are highly plefelred, especially those having molecular weight of from about 1,000 to about 30,000, l,le~efably from about 12,000 to about 30,000.

Chel~tin~ agents beneficially aid cle~ni~ and bleach stability by keeping metal ions, such as calcium, m~nesium, and heavy metal cations in solution. E~camples of suitable chel~ting agents include sodium tripolyphosphate, sodium acid pyrophosphate, tetrasodium pyrophosphate, aminopolycarboxylates such as nitrilotriacetic acid and ethylen~i~minç
tetracetic acid and salts thereof, ethylenP~ mine-N~Nl-disuccinic acid (EDDS) and salts thereof, and polyphosphonates and aminopolyphosphon~tes such as hydroxyeth~ne~liphosphonic acid, ethyle~P~i~mine tetramethylenephosphonic acid, diethylelletf;~...inepe.~ ell.ylenephQsphonic acid and salts thereof. The chP!~ting agent selected is not critical except that it must be comp~tible with the other ingre~lient~ of the denture cleanser when in the dry state and in aqueous solution. Advantageously, the chelating agent con~lises between 0.1 and 60 percent by weight of the composition and preferably between 0.5 and 30 percellt. Phosphonic acid chelating agents, however, preferably co~ ise from about 0.1 to about 1 percent, ~refe.ably from about 0. 1% to about 0.5 % by weight of composition.

E~es suitable for use herein are exemplified by proteases, ~lk~l~ses, amylases, fungal and bacterial lir~es, dextr~n~res, ... ~ es, c~n~ses, esterases, cellulases, pectin~ces~ l~ct~Qes and peroxi~ es, etc. Suitable enzymes are rliscl~sse~l in US-A-3,519,570 and US-A-3,533,139.

The following F~mrles further describe and demonstrate the preferred embo~limPnts within the scope of the present invention.

WO 96/19562 . PCI/US95/15765 EXAMPLES I TO V

The following are f~rese~t~tive denture cle~n~in~ tablets according to the invention. The percentages are by weight of the total tablet. The tablets are made by co~ ressi~g a mixt~re of the gr~m)l~te~ components in a punch and dye tabletting press at a ples~ure of about 105 kPa.

II m 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 Pell,orate Mono~drate 15 12 16 30 15 Pot~c.~illm Mono~e~ ph~te 15 18 13 14 Pyrogenic Silica - 3 Talc 2 EDTMPl FlavorS 2 1 2 1 2 ~ n~soft Fluid4 1 1.5 0.5 2 Bleach I'rec.llsor Agglomerate 9 8 10 12 10 RleaCh rr~c.~rsor A~lomerate I II III IV V
TAED2 2 - 4 5 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.S
1. Ethylçn~li~minetetramethylenephosphonic acid 2. Tetraace~lethylene ~ mine 3. Sodium 3,5,5-trimethylhe~noylo~ybe~.,e..~ sulfonate 4. M~n~coft Fluid - supplied by OSI
S r~pe~l~int-based flavor In F~mples I to V above, the overall tablet weight is 3 g; di~m~ter 25 mm.

The de.llule cle~ncins~ tablets of Px~mrles I to V display improved antiplaque,clçqnci~ and anti-bacterial activity together with e.~cellent cohesion and other physical and in-use pelrolll~ce characteristics.

FXAMP!.F.~ VI TO TX

The following are represeI t~tive perfume, flavour, coolant and antimicrobial compositions according to the invention. The pelce.llages are by weight of total composition.
VI VII vm ~

PPG-5-ceteth-20 3.0 3.0 4.5 3.0 PEG-40 hydroge,lated castor - 1.8 4.5 3.0 oil Tri~leceth-12 2.0 Trideceth 9 2.0 - 3.0 Flavor5 2.0 3.0 Perfume6 - 3.0 T~ c~yl l~ mi-le 0.3 O.S
Triclos-q-n - - 1.0 0.5 ~agnq~oft Fluid4 1.0 1.5 5.0 1.0 Water ~-- -- - to 100%-- ----->

6. relrul~le is a comple.~ mishlre of ingre~iiçnt~ used primarily for - olfactory purposes.

The perfume, flavor, coolant and/or antimicrobial compositions of F~sqmples VI to IX display impfo~ed surface-substantivity, impact and/or efficacy.

Claims (11)

1. A bleach composition comprising an inorganic persalt bleaching agent, a lipophile selected from flavorants, perfumes, physiological coolants, antimicrobial agents and mixtures thereof, and an aminoalkylsilicone having an aminoalkylsiloxane content of from about 0.1%-2% on a repeating unit basis.

2. A composition according to Claim 1 wherein the aminoalkylsilicone is a noncyclic, hydrophobic aminoalkylsilicone having a formula comprising two basic units:

1) (R1)m(R)nSiO(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) (R1)a(R2)bSiO(4-a-b)/2 wherein a+b is 1, 2, or 3, and a and b are integers, wherein R1 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 or wherein R3 is a divalent alkylene of about 1-20 carbon atoms optionally substituted or interrupted by O atoms, R4, R5 and R6 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, preferably from about 5000 to about 100,000.

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 aminoalkyl silicone.

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-(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, 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 an aminoalkylsilicone 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 aminoalkylsilicone is selected from aminoalkylsilicones having an aminoalkylsiloxane content of from about 0.1%-2% on a repeating unit basis.