CA2206457A1 - Oral compositions - Google Patents

Abstract

An oral composition in the form of a toothpaste, powder, liquid dentifrice, mouthwash, denture cleanser, chewing gum or candy comprising one or more oral composition components selected from abrasives, binders, humectants, surfactants, fluoride ion sources, anti-calculus agents and sweeteners and additionally comprising an aminoalkylsilicone having an aminoalkylsiloxane content of from about 0.1 %-2 % on a repeating unit basis. The composition provides improved antiplaque and anti-bacterial activity together with excellent cleansing performance.

Description

CA 022064~7 1997-0~-29 ORAL COMPOSITIONS

TECHNICAL FIELD

The present invention relates to oral compositions such as toothpastes,toothpowders, liquid dentifrices, mouthwashes, denture cleansers, chewing gums, candies and the like. In particular, the invention relates to oral compositions having ~nh~nced antiplaque activity together with excellent cle~n~in~ performance, physical characteristics, and in-use performance characteristics.

BACKGROUND

Plaque is initi~te~l when bacteria adhered to pellicle form a ~roteinaceous film on the surface of teeth. The adherent bacteria metabolize dietary constituents and reproduce and aggregate to form the tenacious deposit known as plaque. Plaque generally consists of bacteria, bacterial end products such as polysaccharides, inorganic salts and salivary proteins.
Plaque bacteria ferment dietary carbohydrates to organic acids which demineralize enamel reslllting in tooth decay.

Calculus is essenti~lly plaque that has been mineralized with calcium phosphates salts. As calculus matures and hardens, it tends to stain noticeably due to adsorption of dietary chromagens. In addition to their unattractive appearance, calculus deposits at the gum line are a contributing source of gingivitis and periodontal dice~se. Besides the hygienic and health problems resulting from plaque, research has shown that the primary source of bad breath is the retention and subsequent degradation of dead cellular material sloughed off continuously by the normal, healthy mouth.

Modern dental hygiene and denture preparations typically contain antiplaque and/or a.~ allar 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.
-CA 022064~7 1997-0~-29 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 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 br~lshin~ for a majority of the population provides optimum plaque forming conditions.

There has been a need, therefore, for developing an oral formulation which has a prolonged, re~iA~ antimicrobial and/or flavor impact effect.

It is known to include silicones in dentifrice compositions, allegedly to coat the teeth and prevent cavities and st~inin~. For instance, GB-A-689,679 discloses a mouthwash cont~ininp an organopolysiloxane for preventing 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 f~cilit~te 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 polysiloxanes are said to be particularly effective. Flavoring oils and/or menthol may be included.

CA 022064~7 1997-0~-29 US-A-3624120 discloses quaternary ammonium salts of cyclic siloxane polymers for use as cationic surfactants, bactericides and as anticariogenic agents.

Accordingly, the present invention provides oral compositions having improved efficacy on plaque, mucil~ginQus and bacterial deposits and which at the same time provides excellent cle~n.~ing performance, physical characteristics, and in-use performance characteristics.

The invention further provides oral compositions cont~ining a lipophilic compound such as a flavorant, physiological cooling agent or antimicrobial, and which has improved substantivity, impact and/or efficacy on teeth and dentures.

SUMMARY OF THE INVENTION

According to a first aspect of the invention, there is provided an oralcomposition in the form of a toothpaste, powder, liquid ~e~tifrice, mouthwash, denture cleanser, chewing gum or candy comprising one or more oral composition components selected from abrasives, binders, humectants, surf~ct~nts, fluoride ion sources, anti-calculus agents and sweeteners and additionally comprising an ~mino~lkylsilicone having an aminoalkylsilo~cane contenl of from about 0.1%-2~ on a repeating unit basis.

Acco~mg to a further aspect of the invention, there is provided an oralcomposition in the form of a toothpaste, powder, liquid ~lentifrice, mouthwash, denture cleanser, chewing gum or candy coLuprising a lipophilic compound selected from flavorants, physiological cooling agents and antimicrobial compounds and an ~mino~lkylsilicone having an aminoalkylsiloxane content of from about 0.1%-2% on a repe~tin~ unit basis.

All percentages and ratios herein are by weight of total composition, unless otherwise indicated.

CA 022064~7 l997-0~-29 The oral compositions of the invention thus comprise an ~mino~lkylsilicone antiplaque agent while preferred compositions additionally comprise a lipophilic compound and/or one or more oral composition components selected from abrasives, binders, hllmectants, surfactants, fluoride ion sources, anti-calculus agents and sweeteners Each of these will be discussed in turn.

In general terms, the ~mino~lkylsilicone is selected from noncyclic, hydrophobic aminoalkysilicones having a formula comprising two basic units:

1) (R1)m(R)nsi0(4-m-n)l2 wherein m+n is 1, 2 or 3; n is 1, 2 or 3;
m is 0,1 ,2; and 2) (R1)a(R2)bSi0(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 substitute~ with fluoro or cyano groups, hydroxy, alkoxy, and acetoxy, for example, wherein R1 and R2 are independently selected from methyl, ethyl, phenyl, vinyl, trifluoro~fopyl and cyanopropyl, and R is --R3--N--R~ or --R3--N-R5 X

wherein R3 is a divalent alkylene of about 1-20, ~refelably about 3-5 carbon atoms optionally sub~ te-l or interNpted by O atoms, R4, RS
and R6 which may be the same or different are selected from H, allyl of about 1-20, ~referably about 1-lQ, more preferably about 1~ carbons optionally substitllte~ or interl.lpted by N and/or O atoms, and X~ is a monovalent anion such as halide, hydroxide, and tosylate, said ~mino~lkylsilicone including from about 0.1-2%, prefelably from about 0.5-2% of unit (1) on a repeating unit basis.

In a preierled embodiment, the aminoalkylsilicones comprise amo-lim~thicones. Amo~imethicones are polydimethylsiloxane polymers CA 022064~7 1997-0~-29 cont~inin~ aminoalkyl groups. The aminoalkyl groups may be present either pen~l~nt or at one or more ends of the polydimethylsiloxane chain.
rleferred are ~mino~lkylsilicones in which aminoalkyl moiety R is selected from (CH2)3NH2, (cH2)3NHc~H2cH2NH2 (CH2)3N(CH2CH2OH)2, (CH2)3NH3+X-, and (CH2)3N(CH3)2(C18H37)+X-, and especially from (CH2)3NH2 and (CH2)3NHCH2CH2NH2. Also preferred are aminoalkyl silicones having an average molecular weight of about 5,000 and above, plerelably from about 5000 to about 100,000, more preferably from about 5000 to about 30,000.

Aminoalkylsilicone compounds suitable for use herein are well known.
Methods of preparing aminoalkylsilicones are given in, for example, US-A-2,930,809.

Examples of amodimethicones include OSI's M~n~eoft fluid. These polymers conlprise aminoalkyl groups affixed to a predomin~ntly polydimethylsiloxane structure. The typical structure of M~gn~coft's aminoalkyl group-cont~ining units is -OSi(Me)C3H6NHCH2CH2NH2.

The aminoalkylsilicone is generally present in a level of from about 0.01 % to about 25 %, ~referably from about 0.1 % to about 5 ~, more ~rereldbly from about 0.5% to about 1.5% by weight.

The oral compositions of the invention pr~fer~bly 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 ~mino~lkylsilicone, ~,~eferably at a level of at least about 1%, more prerelably at least about 5% by weight at 25~C. ~rerelred lipophilic compounds are selected from flavorants, physiological cooling agents and antimicrobial compounds. The aminoalkylsilicone acts to enh~nce the sub~nli~ily of the lipophilic compound to teeth and/or dentures, thereby providing enh~nced and/or sust~ine~l flavor impact and antimicrobial efficacy.

CA 022064~7 1997-0~-29 WO 96/19193 PCT/US9~/16253 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, s~cs~fras 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.

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

Physiological cooling agent suitable for use herein include carbox~milles, menth~ne esters and Ine~th~ne ethers, and mixtures thereof.

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

~X

OR~

where Rs is an optionally hydroxy substihlte~ aliphatic radical cont~inin~
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 T~k~c~o, from T~ c~o International Corporation. A
particularly prefefred cooling agent for use in the compositions of the present invention is T~k~s~P:o 10 [3-1-mPnthoxy ~ropan-1,2-diol (MPD)].
MPD is a monoglycerin derivative of l-menthol and has e~ccellent cooling activity.

CA 022064~7 1997-0~-29 The carbox~mides 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 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.

Compositions in the form of toothpastes, denture cle~ncin~ liquids and pastes and the like will generally comprise a binder or thickenin~ agent.
Binders suitable for use herein include carboxyvinyl polymers, carrrageenan, hydroxyethyl cellulose and water soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose. Natural gums such as gum karaya, ~r~nth~n gum, gum arabic, and gum tr~g~c~nth can also be used. Colloidal m~gn-osi~lm ~hlminllm silicate or finely divided silica can be used as part of the thickening agent to further improve texture. Binders/thickeninE agents can be used in an amount from about 0.1% to about 5.0%, preferably from about 0.1 to about 1% by weight of the total composition.

It is also desirable to include some hllmect~nt material in a toothpaste to keep the composition from har~le~in~ upon exposure to air. Certain hnmect~nts can also impart a desirable sweetness to toothpaste compo~iti~rls. Liquid ~entifrice and moulll~ashes can also contain a ;ly of hnmect~nt Suitable humect~nts include glycerin, sorbitol, xylitol, polyethylene glycols, propylene glycol, other edible polyhydric alcohols, and m~ res thereof. When present, humectants generally r~r~sent from about 10% to about 70%, by weight of the compositions of the invention.

Toothp~stes, liquid dentifrices and denture cleansers in liquid or paste form will generally comprise an abrasive poli~hin~ material. The abrasive poli~hing material contemplated for use herein can be any material which does not excessively abrade dentin or denture acrylic.
These include, for example, silicas including xerogels, hydrogels, aerogels and precipitates, calcium and m~pn~sium carbonates, calcium CA 022064~7 1997-0~-29 ortho-, pyro- meta- and polyphosphates such as dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, and calcium polymetaphosphate, insoluble sodium polymetaphosphate, ~ min~ and hydrates thereof such as alpha ~lllmin~ trihydrate, aluminosilicates such as calcined aluminium silic~te and ~lllminillm silicate, m~nesi~lm and zirconium silic~tes such as nl~nesium trisilicate and thermoseKing polymerised resins such as particulate condensation products of urea and formaldehyde, polymethylmeth~crylate, powdered polyethylene and others such as disclosed in US-A-3,070,510, December 25, 1962 Mixtures of abrasives can also be used. The abrasive poli~hin~ materials generally have an average particle size of from about 0.1 to about 30 microns, prefel~bly from about 5 to 15 microns.

Silica dental abrasives of various types offer exceptional dental cle~nin~
and poliching performance without unduly abrading tooth enamel or dentin. The silica abrasive can be precipitated silica or silica gels such as the silica xerogels described in Pader et al., US-A-3,538,230, issued March 2, 1970 and DiGiulio, US-A-3,862,307, June 21, 1975, for example silica xerogels marketed under the tr~den~me "Syloid" by W. R.
Grace & Company, Davison Chemical Division. Suitable precipitated silica materials include those marketed by the J. M. Huber Corporation under the tr~len~me, "Zeodent", particularly the silica carrying the ~lesi~n~tion "Zeodent 119". These silica abrasives are described in US-A~,340,583, July 29, 1982.

Highly prefe~,~ herein from the viewpoint of providing good cle~n~in~
pelror~a~ce combined with excellent comp~tibility with the antiplaque agent are calcium carbonate abrasives.

The abrasive is generally present in dentifrice formulations of the invention at a level of from about 10% to about 70%, preferably from about 15 % to about 25 % by weight.

The present compositions can also contain surf~ct~nts. Suitable surf~ct~n~s are those which are reasonably stable and foam throughout a wide pH range, including non-soap anionic, nonionic, cationic, zwiKerionic and amphoteric organic synthetic deler~ents. Many of these CA 022064~7 1997-0~-29 suitable agents are disclosed by Gieske et al. in US-A-4,051,234, September 27, 1977.
-Examples of suitable surfactants include alkyl sulfates; condensationproducts of ethylene oxide with fatty acids, fatty alcohols, fatty amides, polyhydric alcohols (e.g. sorbitan monostearate, sorbitan oleate), aL~yl phenols (e.g. Tergitol) and polypropyleneoxide or polyoxybutylene (e.g.
Pluronics); amine oxides such as dimethyl cocamine oxide, ~im~thyl lauryl amine oxide and cocoalkyldimethyl amine oxide (Aromox);
polysorbates such as Tween 40 and Tween 80 (Hercules); sorbitan stearates, sorbitan monoaleate, etc; sarcosin~tes such as sodium cocoylsarcosinate, sodium lauroyl sarcosinate (Hamposyl-95 ex W. R.
Grace); cationic surfactants such as cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl-dimethyl benzyl ammonium chloride and coconut alkyl trimethyl ammonium nitrate A soluble fluoride ion source can also be incorporated in the present compositions. The soluble fluoride ion source is used in amounts sufficient to provide from about 50 to about 3500 ppm of the fluoride ion.
rrere~led fluorides are sodium fluoride, stannous fluoride, indium fluoride, zinc ammonium fluoride, tin ammonium fluoride, c~lcillm fluoride and sodium monofluorophosphate. Norris et al., US-A-2,946,735, issued July 26, 1960 and Widder et al., US-A-3,678,154, issued July 18, 1972 disclose such salts as well as others.

The present compositions can also include an anti-calculus agent.
Suitable anti-calculus agents include the di- and tetra-alkali metal pyrophosphates as set out in EP-A-097476. Specific salts include tetra alkali metal pyrophosphate, .li~lk~li metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the alkali metals are sodium or potassium. The salts are useful in both their hydrated and unhydrated forms. The amount of pyrophosphate salt useful in these compositions is any effective amount and is generally enough to provide in composition at least 1.0% P2074, preferably from about 1.5% to about 10%, more ~lcferably from about 3% to about 6% by weight of composition. The pyrophosphate salts are described in more CA 022064~7 1997-0~-29 detail in Kirk & Othmer, Encyclopedia of Chemical Technolo~y, Second Edition, Volume 15, Interscience Publishers (1968).

Other anti-calculus agents suitable herein are zinc salts. Zinc salts are disclosed in US-A~,100,269, US-A~,416,867, US-A-4,425,325 and US-A-4,339,432. A prefelled agent of the zinc variety is zinc citrate. Zinc compounds can be present in amounts sufficient to provide from about 0.01 % to about 4%, prefer~bly from about 0.05% to about 1 % by weight of zinc ion.

Other suitable anti-calculus agents include the synthetic anionic polymers (including polyacrylates and copolymers of maleic anhydride or acid and methyl vinyl ether (eg Gantrez) as described in US-A~,627,977, polyamino propane sulfonic acid, polyphosphates (eg tripolyphosphate, hexametaphosphate), diphosphonates (eg EHDP, AHP), polypeptides ( eg polyaspartic and lpoly~ t~mic acids), and mixtures thereof.

Sweetening agents which can be used include aspartame, aceslllf~m~, saccharin, de~trose, levulose and so~lium cycl~m~te. Sweetenin~ agents are generally used at levels of from about 0.005% to about 2% by weight of composition.

Other optional components for use herein include water-soluble antibacterial agents, such as chlorhexidine digluconate, quaternary ammonium antibacterial compounds and water-soluble sources of certain metal ions such as zinc, copper, silver and stannous (e.g., zinc, copper and stannous chloride, and silver nitrate); piFm~nts such as li~niunl dio~cide; orally acceptable dyes/colorants such asFD&C Blue #1, FD&C
Yellow #10, FD&C Red #40; antio~ nts~ vit~min~ such as vitamin C
and E, other antiplaque agents such as stannous salts, copper salts, ~lfolllium salts and m~nesium salts; pH adjusting agents, ~ntic~ries agents such as urea, calcium glycerophosphate, sodium trimetaphosphate, plant e~tracts, desensitizing agents for sensitive teeth such as pot~sil~m nitrate and pot~si~lm citrate, and mi~ctures thereof.

Typically, moulh~ashes comprise a water/alcohol solution, llavor, humectant, sweetener, sl)d~inE agent, and colorant as described above.

CA 022064~7 1997-0~-29 Mouthwashes can include ethanol at a level of from 0 to 60%, preferablyfrom S to 30% by weight.

Denture cleanser compositions of the invention can additionally includeone or more bleaching agents, 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 denture cleansers such as the alkali metal and ammonium persulfates, perborates, percarbonates and perphosphates and the alkali metal and ~lk~line earth metal peroxides. Examples of suitable bleaching agents include potassium, ammonium, sodium and lithium perslllf~te~ and perborate mono- and tetrahydrates, sodium pyrophosphate peroxyhydrate and m~n~sium, calcium, strontium and zinc peroxides. Of these, however, the alkali metal persulfates, perborates and mixtures thereof are ~re~ered for use herein, highly preferred being the alkali metal perborates. In~ee~l, it is a feature of the invention that the tablet compositions herein will provide excellent antimicrobial activity even in the absence of alkali metal perslllf~tes.

The amount of ble3chin~ agent in the total composition is generally *omabout S to about 70% ~refeldbly from about 10% to about 50%. In compositions comprising a mixture of alkali metal perslllf~tes and perborates, the overall persulfate:perborate ratio is suitably from about 5:1 to about 1:5, more especially from about 2:1 to about 1:2.

The denture cle~n~in~ compositions can also incorporate an effervescence generator, ie a material which in the presence of water releases carbon dio~cide or o~ygen with effervescence. The effervescence generator can be selected from generators ~,vhich are effective under acid, neutral or ~lk~line 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 ~1k~line 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, CA 022064~7 1997-0~-29 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, fumaric, citric, malic, maleic, gluconic, succinic, salicylic, adipic or sulphamic acid, sodium fumarate, sodium or potassium acid phosphates, betaine hydrochloride or mixtures thereof. Of these, malic acid is ~refelled. Effervescence generators which are effective under ~lk~line pH conditions include persalts such as alkali and ~lk~line 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, pot~si~lm sulphate and potassium bisulphate and which has an active oxygen content of about 4.5 % .

In preferled denture cle~n~ing compositions in tablet form, the effervescence generator takes the form of a solid base material which in the presence of water releases carbon dioxide or oxygen with effervescence. Suitably, 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 cle~nin~ and ~ntimicrobial activity. The (bi)carbonate 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~o to about 30% of the total composition.

The denture cle~nsin~ compositions of the invention can be supplemente~by other known components of such form~ tions. An especially prere~led additional component is an organic peroxyacid 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.

CA 022064~7 1997-0~-29 A test solution is prepared by dissolving the following materials in 1000 mls distilled water:

sodium pyrophosphate (Na4P2O7- 10H20) 2.5g sodium perborate (NaBO2.H2O2.3H2O) having 10.4% available oxygen 0.615g sodium dodecylben~
sulphonate O.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 m~int~in~ at 60~C. After S mim1tes from addition, a 100 ml portion of t_e solution is withdrawn and imme~ te1y 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 cont~ining one or more acyl groups, which are susceptible to perhydrolysis. The prererred 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 substitute~l hydrocarbon group having ~refe~ably from about 1 to about 20 carbon atoms.
Fx~mrles of suitable peracid precursors include:

1) Acyl organoamides of the formula RCONR1R2, where RCO is carboxylic acyl radical, R1 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 - diacetyl~niline and N-acetylphth~limic~e;

CA 022064~7 1997-0~-29 W O 96/19193 PCT~US95/16253 b) N-acylhydantoins, such as N,N ' -diacetyl-5,5-dimethylhydantoin;
c) Polyacylated alkylene ~ mines, such as N,N,N'N' -tetraacetylethylenedi~mine (TAED) and the corresponding hexamethylene~i~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~mi~le and N-phenyl-N-acetyl menthane sulphon~mi~le, as disclosed in GB-A-3,183,266.

3) Carboxylic esters as disclosed in 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, acet.yl 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) Carbo~cylic esters having the gernal formal Ac L wherein Ac is the acyl moiety of an organic carboxylic acid comprising an optionally substit~lte~l, linear or branched C6-C20 alkyl or alkenyl moiety or a C6-C20 alkyl-subs~ ed 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 oxyben7enesulfonate or oxybenzoate. rrerelred 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, preferably 6 to 12, more preferably 7 to 9 carbon atoms and wherein the longest linear alkyl chain e~t~n~in~ from and including the carbonyl carbon contains from 5 to 18, prefel~bly 5 to 10 carbon atoms, R3 optionally being substit~lted (preferably alpha to the carbonyl moiety) by _ CA 022064~7 l997-0~-29 W O 96/19193 PCT~US95/16253 Cl, Br, OCH3 or OC2Hs. Examples of this class of material include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5-trimethylhexanoyloxybenzoate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxybenezenesulfonate, the acyloxy group in each inct~nce preferably being p-substitute~l;

b) Ac has the formula R3(AO)mXA wherein R3 is a linear or branched alkyl or alkylaryl group cont~inin~ from 6 to 20, ,rererably from 6 to 15 carbon atoms in the alkyl moiety, Rs being optionally substituted by Cl, Br, OCH3, or OC2Hs, AO
is oxyethylene or oxypropylene, 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~ining 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 derivatives of the formula R30CO(CH2)2COL, glycollic acid derivatives of the formula R30CH2COL, hydroxypropionic acid derivatives of the formula R30CH2CH2COL, oxalic acid derivatives of the formula R30COCOL, maleic and fumaric acid derivatives of the formula R30COCH=CHCOL, acyl aminocaproic acid derivatives of the formula R3CONR1(CH2)6COL, acyl glycine derivatives of the formula R3CONR1CH2COL, and amino-6-oxocaproic acid derivatives of the formula R3N(Rl)CO(CH2)4COL. In the above, m is preferably from O to 10, and R3 is prefelably C6-C12, more preferably C6-Clo alkyl when m is zero and Cg-C1s when m is non-zero. The leaving group L is as defined above.

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

CA 022064~7 1997-0~-29 6) Optionally substituted anhydrides of benzoic or phthalic acid, for example, benzoic anhydride, m-chlorobenzoic anhydride and phthalic anhydride.

Of all the above, prefefred are organic peracid precursors of types l(c) and 4(a).

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 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 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 surf~ct~nte, fatty acids, so~linm carboxymethyl cellulose, gelatin, fa~ty alcohols, phosphates and polyphosphates, clays, aluminosilicates and polymeric polycarboxylates. Of the above, polyethyleneglycols are highly preferled, especially those having molecular weight of from about 1,000 to about 30,000, prefeldbly 2000 to about 10,000.

rrercl~d from the viewpoint of opti.llulll dissolution and pH
characteristics are bleach precursor agglomerates which comprise from about 10% to about 75%, ~re~dbly from about 20% to about 60% by weight thereof of peroxyacid bleach precursor, from about 5 % to about 60% prefel~bly from about 5% to about 50%, more prt;rt;lably from about 10% to about 40~o of a (bi) carbonate/acid effervescent couple, from about 0% to about 20% of a peroxoboroate, and from about 5% to about 40%, prefelably 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 being valuable from the viewpoint of optimum dissolution CA 022064~7 1997-0~-29 performance and aesthetics. The level of bleach precursor agglomerates, moreover, is pleferably from about 1% to about 20%, more preferably from about 5% to about 15% by weight of composition.

The denture cle~n~inE compositions of the invention can be in paste, tablet, granular or powder form, although tablet-form compositions are highly preferred herein. Compositions in tablet form can be single or multiple layered tablets.

Denture cle~n~in~ compositions of the invention can be supplemente~ by other usual components of such formulations, especially surfactants, chelating agents, enzymes, flavorants, physiological cooling agents, antimicrobial compounds, 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. The free moisture content of the final composition is desirably less than about 1% and especially less than about 0.5%.

Tablet binders and fillers suitable for use herein include polyvinylpyrrolidone, poly (oxyethylene) of molec~ r 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, gelatin, fatty alcohols, clays, polymeric polycarboxylates, sodium carbonate, calcium carbonate, calcium hydroxide, m~nesillm o~cide, m~neSium 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 ~refelled, especially those having molecular weight of from about 1,000 to about 30,000, l,ref~lably from about 12,000 to about 30,000.

The surface active agent used in the denture cle~ncin~ compositions of the invention can be selected from the many available that are compatible with the other ingre~ients of the denture cleanser, both in the dry state and in solution. Such materials are believed to improve the effectiveness -CA 022064~7 1997-0~-29 of the other ingredients of the composition by aiding their penetration into the interdental surfaces. Also, these materials aid in the removal of food debris attached to the teeth. Between 0.1 and ~ percent by weight of the dry composition of a dry powder or granular anionic surface active agent, such as sodium lauryl slllf~te, sodium N-lauroylsarcosinate, sodium lauryl sulfo~cet~te or dioctyl sodium sulfosuccinate or ricinoleyl sodium sulfosuccinate, may, for example, be included in the composition and preferably the surface active agent comprises between 0.5 and 4 percent of the composition.

Suitable cationic, non-ionic and ampholytic surface active agents include, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide, condensation products of alkylene oxides such as ethylene or propylene oxide with fatty alcohols, phenols, fatty amines or fatty acid alkanolamides, the fatty acid alkanolamides themselves, esters of long-chained (Cg-C22) faKy acids with polyalcohols or sugars, for example glycerylmonostearate or saccharosemonolaurate or sorbitolpolyoxyethylenemono-or di-stearate, betaines, sulphobetaines or long-chain alkylaminocarboxylic acids.

Chelating agents beneficially aid cleaning and bleach stability by keeping metal ions, such as calcium, magnesium, and heavy metal cations in solution. F.~mples of suitable chelating agents include sodium tripolyphosphate, sodium acid pyrophosphate, tetrasodium pyrophosphate, aminopolycarbo~cylates such as nitrilotriacetic acid and ethylene~ mine tetracetic acid and salts thereof, and polyphosphonates and aminopolyphosphonates such as hydroxyeth~n~iphosphonic acid, ethylen~li~mine tetramethylenephosphonic acid, diethylenetri~minto.pent~methylenephosphonic acid and salts thereof. The chelating 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 chelating agent comprises between 0.1 and 60 percent by weight of the composition and preferably between 0.5 and 30 percent. Phosphonic acid chelating agents, however, ~re~rably comprise from about 0.1 to about 1 percent, preferably from about 0.1 % to about 0.5% by weight of composition.

WO 96/191~3 PCT/US95/16253 Enzymes suitable for use herein are exemplified by proteases, ~lk~ es, amylases, lipases, dextranases, mutanases, glucanases etc.

The following Examples further describe and demonstrate the preferred - embodiments within the scope of the present invention.

EXAMPLES I TO V

The following are represe~t~tive denture cle~n~ing tablets according tothe invention. The percentages are by weight of the total tablet. The tablets are made by colllpressing a mixture 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 22 25.2 25 13.9 23 Sodium Perborate Monohydrate 15 12 16 30 15 Potassium Monopersulphate 15 18 13 - 14 Pyrogenic Silica - 0.3 0.1 0.1 Talc 2 EDTMPl FlavorS 2 1 2 1 2 M~gn~oft Fluid4 1 1.5 5 10 Bleach Precursor Agglomerate 9 8 10 12 10 Bleach Precursor A~plomerate I II III IV V
TAI~D2 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. Ethylene~ min~tetramethylenephosphonic acid 2. Tetraacetylethylene ~ min~
3. Sodium 3,5,5-trimethylhexanoyloxyben7ene sulfonate 4. Magnasoft Fluid - supplied by OSI
5 Peppermint-based flavor W O 96/19193 PCT~US95/162S3 2 ~

In Examples I to V above, the overall tablet weight is 3 g; diameter 25mm.

The denture cle~n~in~ tablets of Examples I to V display improved antiplaque,cle~n~ing and anti-bacterial activity together with excellent cohesion and other physical and in-use performance characteristics.

EXAMPLES VI TO VIII

The following are representative toothpaste/denture cle~n~in~ pastes according to the invention. The percentages are by weight of total composition.

VI VII VIII
Calcium Carbonate 20 25 15 Glycerine 10 12 8 Sodium CMC 3.5 3 4 Titanium Dioxide 0.7 0.5 0.6 Methyl/Propyl Parabens 0.1 0.1 0.1 Sodium Saccharin 0.3 0.4 0.2 Flavor5 1 1 2 oft Fluid4 1 1.5 0.5 Trichlosan - 0-5 Water To 100 The toothpastes/denture cle~n.cin.~ pastes of Examples VI to VIII display in~roved antiplaque, flavor impact and anti-bacterial activity together with excellent cle~n~in~ characteristics.

Claims (9)

WHAT IS CLAIMED IS:

1. An oral composition in the form of a toothpaste, powder, liquid dentifrice, mouthwash, denture cleanser, chewing gum or candy comprising one or more oral composition components selected from abrasives, binders, humectants, surfactants, fluoride ion sources, anti-calculus agents and sweeteners and additionally comprising 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 comprising from about 10% to about 70% by weight of a dental abrasive selected from silica, alumina, aluminosilicates, magnesium and zirconium silicates, calcium ortho-, pyro- meta- and polyphosphates, calcium and magnesium carbonates, insoluble metaphosphates and thermosetting polymerised resins.

6. A composition according to any of Claims 1 to 5 comprising an amount of a fluoride ion source sufficient to provide from 50ppm to 3500ppm of fluoride ions.

7. A composition according to any of Claims 1 to 6 comprising from about 0.1% to about 1 % by weight of a binder.

8. Use of an aminoalkylsilicone as antiplaque agent in an oral composition, wherein the the aminoalkylsilicone has an aminoalkylsiloxane content of from about 0.1 %-2% on a repeating unit basis.

9. Use according to Claim 8 wherein the oral composition is a denture cleansing composition.