CA1084846A - Zinc salt and anionic polymer to control mouth odor - Google Patents
Zinc salt and anionic polymer to control mouth odorInfo
- Publication number
- CA1084846A CA1084846A CA277,803A CA277803A CA1084846A CA 1084846 A CA1084846 A CA 1084846A CA 277803 A CA277803 A CA 277803A CA 1084846 A CA1084846 A CA 1084846A
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- polymer
- composition
- anionic
- same meaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic
Abstract
Abstract of the Disclosure A novel composition to prevent and control mouth odor, which is also effective in preventing calculus, plaque, caries and periodontal disease containing as the essential agent, a zinc-polymer combination formed by the reaction or interaction of a zinc compound with an anionic polymer containing carboxylic, sulfonic and/or phosphonic acid radicals.
Description
10848~6 This invention relates to novel oral formulations comprising a combination of a zinc compound and an anionic polymer as an effective agent against mouth odor, plaque calculus and periodontal disease.
The prior art is replete with oral compositions con- -taining zinc salts such as zinc chloride, zinc iodide, zinc fluoride, zinc sulfide, zinc phenol sulfonate and the like as antiseptic agents, and correctives of oral conditions such as pyorrhea. Zinc chloride has commonly been used in oral formulations for its astringency propertiesO Zinc phenol sulonate has been utilized in the prior art dentifrice compositions as an anti-plaque and anti-calculus agent as well as an odor inhibitor of fermentation and putrefaction which occurs in the oral eavity. These soluble zinc salts have the dual disadvantage of leaving an unpleasant astringent taste in the mouth as well as having short-lived efficacy against plaque, calculus and as an odor inhibitor.
Sparingly soluble zinc salts such as zinc citrate; zinc ;~
C14-alkyl maleate, zinc benzoate, zinc caproate, zinc carbonate, r ' ..~' zinc citrate, etc. have been used in dentifrice formulations !' to prolon~ the anti-calculus and anti-plaque effectiveness of the zinc ions due to the slow dissolution of the zinc ¦¦salts in the saliva. The sparingly soluble characteristic 'lof these zinc salts promotes longevity of action against plaque and calculus at the expense of initial or immediate efficacy.
The use of a zinc co~plex of a specific diketone as an j agent for cornbating tartar and tooth discoloration is also lo 'known, as set forth in German ~atent No. 2,229,466. Thus, it ! iS apparant that zinc compounds generally are known to have 'deodorizing properties as well as efficacy against plaque, calculus and possibly yeriodontal disease.
I~ Also known is the use of a water soluble sodium salt ,of a linear anionic polymer as an anti-calculus agent, as set ~forth in ~.S. Patent No. 3,429,963 to Shedlovsky. This patent ~discloses that the hydrolyzed copolymers and/or polymers iprevent the deposition of calculus by means of their calcium sequestration properties. However, there is no suggestion in Ijthis patent, nor in any of the known prior art, that a combination of a zinc salt and an anionic polymer is unusually effective in preventing and controlling mouth odor while simultaneously preventing calculus, plaque, caries and peri-~odontal disease.
Accordingly, it is an object of this invention to provide an oral composition containing as the mouth odor inhibitor, the reaction product of a zinc salt with an anionic polymer-Another object of instant invention is to provide an
The prior art is replete with oral compositions con- -taining zinc salts such as zinc chloride, zinc iodide, zinc fluoride, zinc sulfide, zinc phenol sulfonate and the like as antiseptic agents, and correctives of oral conditions such as pyorrhea. Zinc chloride has commonly been used in oral formulations for its astringency propertiesO Zinc phenol sulonate has been utilized in the prior art dentifrice compositions as an anti-plaque and anti-calculus agent as well as an odor inhibitor of fermentation and putrefaction which occurs in the oral eavity. These soluble zinc salts have the dual disadvantage of leaving an unpleasant astringent taste in the mouth as well as having short-lived efficacy against plaque, calculus and as an odor inhibitor.
Sparingly soluble zinc salts such as zinc citrate; zinc ;~
C14-alkyl maleate, zinc benzoate, zinc caproate, zinc carbonate, r ' ..~' zinc citrate, etc. have been used in dentifrice formulations !' to prolon~ the anti-calculus and anti-plaque effectiveness of the zinc ions due to the slow dissolution of the zinc ¦¦salts in the saliva. The sparingly soluble characteristic 'lof these zinc salts promotes longevity of action against plaque and calculus at the expense of initial or immediate efficacy.
The use of a zinc co~plex of a specific diketone as an j agent for cornbating tartar and tooth discoloration is also lo 'known, as set forth in German ~atent No. 2,229,466. Thus, it ! iS apparant that zinc compounds generally are known to have 'deodorizing properties as well as efficacy against plaque, calculus and possibly yeriodontal disease.
I~ Also known is the use of a water soluble sodium salt ,of a linear anionic polymer as an anti-calculus agent, as set ~forth in ~.S. Patent No. 3,429,963 to Shedlovsky. This patent ~discloses that the hydrolyzed copolymers and/or polymers iprevent the deposition of calculus by means of their calcium sequestration properties. However, there is no suggestion in Ijthis patent, nor in any of the known prior art, that a combination of a zinc salt and an anionic polymer is unusually effective in preventing and controlling mouth odor while simultaneously preventing calculus, plaque, caries and peri-~odontal disease.
Accordingly, it is an object of this invention to provide an oral composition containing as the mouth odor inhibitor, the reaction product of a zinc salt with an anionic polymer-Another object of instant invention is to provide an
-2-. _ .. . . _ _ __.. _ , .
484~
oral composition effective in inhibiting mouth odor over a protracted period of time.
Still another object of this invention is to provide an oral com-position effective in inhibiting plaque, calculus, caries and periodontal disease.
It has been found, through radioisotope studies, that anionic polymers can be adsorbed onto oral surfaces. Accordingly, an effective method of controlling mouth odor entails the use of an oral composition comprising a zinc polymer salt or complex formed by combining zinc compounds with anionic polymers. The positively charged zinc ions can react with the poly-meric carboxyl, sulfonic or phosphonic acid groups of the anionic polymers to form zinc-polymer combinations. In the presence of excess acidic groups, the zinc-polymer combinations adsorb onto the oral surfaces such as the teeth and oral mucosa, thereby forming a reservoir of zinc ions capable of being gradually released with time into the oral environment.
According to the present invention, there is provided a non-astringent tasting oral composition capable of countering mouth odor, compris-ing effective amounts of a combination of a zinc compound and an anionic polymer containing carboxylic, sulfonic or phosphonic acid radicals. Said zinc-polymer combinations provide both a means of attachment to the oral cav-ity as well as form a reservoir of zinc ions which are gradually released over a protracted period of ~ime as an effective means to combat mouth odor, pla~ue, calculus, and periodontal disease. In addition, the zinc-polymer combinations decrease the high astringency which is characteristic of zinc ions, thereby leaving a more pleasant taste in the mouthO
It has been ascertained through equilibrium dialysis ...
.. ... .
:
... .
108484~
', , i ' studies against water that the zinc ions are bound tothe ianionic polymer and are slowly released with time as clearly indicated by the results in Table I, wherein 0. 025% zinc oxide llplus 2,',~ of a copolymer of vinyl methyl ether and maleic ~lanhydride having a molecular weight of 250~ 000 (Gantrez 119) I ,!was tested against zinc oxide per se.
1,l ,l Table I
Equilibrium Dial~sis Studies l Rate of Dissociation 10 , _ Coml~ound 10 Min 1 Hr 24 Hrs ~Zn 2 ~ Gantreztll9 * 0 0 53 ,zn+2 ~ H20 21 70 100 . ' ~
Ij j * 0. 025~o zinc oxide + 2~o Gantrez 119 ; pH adjusted to 6~5 with ** 0~ 025~ zinc oxide t lN HCl ; pH adjusted to 6 ~ 5 with 3N NH40H
I
The above table clearly shows that no zinc was detected in the dialysate (ou-tside membrane) after 10 minutes, and after 1 hour of dialysis; and only ~3~o zinc was found in the ', ,Idialysate after 24 hours dialysis. Whereas, in the absence of ,,the polymer, 21~ zinc was detected in the dialysate after ', ' '.only 10 minutes, 70~ zinc was found after only 1 hour and lOO~o .zinc was found in the dialysate after 24 hours dialysis. In '.'the presence of saliva salts, the zinc ions are bound to the ¦
'Ipolymer and are even more gradually released wi~h time, with "only 7~ zinc being detected in the dialysate after 24 AurS.
''t Trademark ., -4-., ~
"
,' ' 10848~6 , In contrast, in the absence of the polymer, thezinc is dialyzed ~out ~% after 10 minutes; 50% after 1 hour; and lOO~o after 24hours.
~l 'l'he anionic polymers are well known in the art. Prefer-ably, the polymer is one which is linear and water-soluble.
For example, it may be soluble in water, when in its sodium or ammonium salt form, at least to i;he extent of the concen- ¦
tration in which it is employed ( O. l~o to lO~o) . See for instance lithe anionic polymeric materials described in U.S. No. 2,984,639, lo 3,325,402, 3,429,963, the article on "Polyelectrolytes" in Vol. 10 of Encyclopedia of Polymer Science pages 781 ff, particularly pages 781, 782 and 784 listing various poly-electrolytes. The anionic polymers employed herein preferably ~ contain ionizable carboxyl, sulfonic or phosphonic groups. A
preferred type of polymers has its ionic substituents on a polymer chain which is hydrocarbon preferably aliphatic ~hydrocarbon (e.g. a vinyl polymer). Typical of such anionic polymers are copolymers of an unsaturated polybasic carboxylic lacid or anhydride thereof (preferably dibasic and having 4 carbon atoms per molecule) and of an olefin having 2 or more carbon atoms per molecule; polyolefin sulfonates; polyolefin phosphonates; and polyolefin phosphates, the olefin group -~
containing 2 or more carbon atoms. Suitable examples include~ !
' 1. A copolymer of maleic anhydride with ethylene, or 25 i styrene, or isobutylene, or polymethyl vinyl ether, or , polyethylvinyl ether, having recurring ~roups:
; ' X ff H---CH
¦! OOM COOM1 ' wherein ~ and r~!1 are individual~y hydrogen, sodium, potassium .~ -5-~, , I
__ ... ._._. ~, 'lor arnrnoniu~n and may be the same or different, and X is ethylene, styrene, isobutylene, methylvinyl ether, and ! ethylvinyl ether.
Il 2. A polyacrylic acid and polyacrylates thereof having 5 It recurring groups: ¦
¦~ _ CH------CH2 IH CH2 ¦I COO~ COOM
,~wherein M and ~1 have the same meaning as above.
Il 3. A polyitaconic acid and polyitaconates thereof 10 llhaving recurring groups: ~' ~H2 ff O~M
{~H2 OOM
, 1 ~'wherein M and ~1 have the same meaning as above.
ll 4. A polyolefin sulfonate having recurring groupss CH - CH
0=~=0 I OM
~,wherein M has the same meaning as above.
5, A polyvinyl phosphonate having recurring groups:
i ii MO-~=o . ' OMl !
~ j 6, A polyvinyl phosphate having recurring groups- i , ,, ~
' MO-P~O
~M 1 , _ . , .
1~3848~6 .
I
~Good results have been obtained with anionic polymers of very high molecular weight such as about 500~000 or 1,O00,000 as well as of relative]y low molecular weights of at least l,OO0 'land preferably 1,500 to 500,000. The anionic polymer consti-~tutes about 0.1 to 10~ by weight and preferably 0~5-1~5yo of the oral composition.
The zinc compounds that form the zinc-polymer combination by reaction or interaction with said anionic polymer may be any physiologically acceptable zinc salt including the water soluble and insoluble, organic and inorganic zinc salts.
Any zinc compound equivalent to 1.5 mFI/ml zinc may be mixed with the anionic polymer. Examples of suitable zinc compounds that may be employed includes ,'~zinc acetate zinc isovalerate 15~ 'zinc acetylacetonate zinc D-lactate zinc ammonium sulfate zinc DL-lactate zinc benzoate zinc laurate i r zinc bromide zinc hexafluorosilicate zinc beryllium orthosilicate zinc methacrylate zinc borate zinc molybdate 'zinc butylphthalate zinc naphthenate zinc butylxanthate zinc octoate ~' zinc caprylate zinc oleate ; zinc carbonate zinc orthophosphate zinc chloroanilate zinc phenolsulfonate ~ zinc chlorate zinc pyridine-2-thiol-1-oxide I zinc chromate zinc pyrophosphate , zinc citrate zinc resinate i zinc cyclohexanebutyrate zinc salicylate ~ -7-' i .
zinc chlori~ zinc sulfate zinc ~allate zinc nitrate zinc fluoride zinc selenide zinc alpha-glucoheptonate zinc stearate zinc gluconate zinc sulfanilate zinc glycerophosphate zinc tartrate zinc hydroxide zinc tellurate zinc ~-hydroxyquinoline zinc tungstate ,zinc 12-hydroxystearate zinc valerate 10 ~!zinc iodide zinc vanadate zinc acrylate zinc tribromosalicylanilide zinc oxide zinc ricinoleate ;zinc propionate '~Although the majority of ~e zinc salts might have limited solubility in water, the presence of the anionic polymer does increase the solubility of the combinction. Zinc oxide or zinc ~propionate, for example, are insoluble in water but in the presence of adequate amounts of the anionic polymer they are Ijsolubilized. The pH thereof can be adjusted to ~.5 to 7.0 `with dilute NH40H and the clarity of the solutions are retained.
~,any insoluble zinc salts are rendered soluble when combined with the anionic polymers, thereby providing a means of following the interaction or reaction between zinc and the anionic polymer. The zinc compound constitutes about .01-5%
~5 and preferably .025-1~ by weight of the oral composition.
The solubility of the zinc-polymer combination appears to be a factor in the activity against odor formation. Soluble conlbinations of anionic polymer and zinc salt aEe very effective in inhibiting odor formation, whereas insoluble zinc-!~olymer combinations are less effective in reducing odor Ii i , . _ formation. Soluble combinations of the anionic polymer withzinc oxide, or zinc propionate are very effective in inhibiting VSC (volatile sulfur compoun~),whereas the insoluble zinc-polymer combinations such as polymer ~ zinc pyrophosphate, zinc ~lycerophosphate, or zinc, 8-OH quinoline were ineffective or only slightly effective.
Another factor which influences the efficacy of the zinc-poly~er comb~ion as an odor-inhibitor is the counterion in the original zinc compound. The zinc gluconate, and zinc alpha-glucoheptonate polymer combinations are soluble but substantially inactive in reducin~ mouth odor. The zinc salicylate-~olymer combinations are possibly effective a~ainst , ..
periodontal disease because of the anti-inflammatory properties of the salicylate counterion in addition to the benefit from ' 15 the zinc ions of the suppression of mouth odor. I
Aqueous solutions and dispersions of various zinc compounds were tested in an in vitro system co~sting of whole ,human saliva, L-cysteine as substrate, and incubated for 3 , hours at 37C in an airtight container. After incubation, ~ithe headspace VSC (volatile sulfur compoun~)formation was ,,measured by an instrumental GC-flame photometric technique.
Since mouth odor has been attributed to the presence of ` volatile sulfur compounds such as hydrogen sulfide, methyl mercaptan and dimethyl sulfide resulting from putrefactive processes occuring in the oral cavity, aforesaid in vitro test provide results comparable to in vivo sensory evaluations.
The results, as set forth in ~able II, show excellent VSC
inhibition for the zinc oxide, zinc chloride and zinc propionate combinations with the anionic polymer. Zinc chloride plus water was used as the control compound.
!
.
.
~084846 Table II
Com~ound *~O VSC Inhibition Zinc oxide + G-1191 (soluble) 52 ¦
;IZinc chloride + G-119 (soluble) 36 5 IZinc propionate + G-ll9 (soluble) 53 Zinc gluconate + G-119 (soluble) f 15 IlZinc alpha-glucoheptonate + G-119 (soluble) 15 : Zinc pyrophosphate (insoluble) f 12 .Zinc glycerophosphate + G-ll9 (slightly soluble) 13 lo iZinc 8-OH quinoline + G-119 (slightly soluble) 24 ,l Zinc salicylate + G-119 (soluble) - 17 .
~ Zinc chloride + H20 54 . I
' ' ', ~ Zinc equivalent to 1.6 mg/ml: G-ll~ - 0.1%; pH between 6.5 to !~ 7 ~ ~
- 15 , 1 G-ll9 is the anionic polymer defined in Table I
`. f indicative of promotion of odor formation as opposed to : inhibition .
In addition to the efficacy of the zinc-polymer combina-tions as a mouth odor inhibitor, the taste thereof is distinctly ;different from, and an improvement over, that of zinc chloride as evidenced by a testing program wherein a panel of five persons tasted two samples, via a mouthrinse, containing , _, _ .
equivalent concentrations of zinc ions; one sample containing t Izinc chloride/poly~er combination and the other containing zinc chloride/water plus 0.2% flavor(both at a pH between 5.5-5.~). The participants agreed, without exception, that 5 the two samples were distinctly different and that the zinc 'Ichloride-polymer sample had very little of the astringent, jmetallic taste characteristic of zinc ions. These results show that the presence of the polymer improves the taste f ! ;i zinc-containing solutions by eliminating the astringent taste lO jland the numbing of the tongue attributable to the zinc ions.
~Thus, it is apparent that the zinc-polymer combinations are ;particularly useful in formulations where the taste of zinc creates a disadvantage.
Aqueous dispersions or solutions of zinc-polymer com-15 bination may be produced by adding a zinc salt in the form of ~a dilute solution, a paste or in the dry state, to a dilute solution of anionic polymer, and stopping the addition before the amount of zinc salt is such as to form a precipitate or gel. With good agitation and careful addition not to exceed 20 the amount of maximum solubility of the zinc-polymer complex, a clear solution or dispersion is obtained. This phenonema 'is clearly indicated in Example 2. The anionic polymer solution is preferable adjusted to a pH of about 5,5 with ~iammonium hydroxide or other suitable base prior to the addition 25 of the zinc salt. The pH of the final zinc polymer salt solution is about 4.5-6.o. For example, a suitable zinc polymer salt or complex is formed by adding 0.050M of a zinc salt to 500 ml of a 2~o solution of a copolymer of methylvinyl ether and maleic anhydride, (adjusted to a pH of 5,5 with 3N
30 ammonium hydroxide) and mixing well. The final solution or ., I
. . .
' 1084846 , '.
! disZpersi.on of the zine-anionic polymer complex preferably has a pH of abou-t 4.5-6.o. lt is believed th~t the ionized ~carboxyl groups react or interact with the zinc ion to form a zinc-polymer salt or complex. See the article by Crisp et lal, J Dent Res March-April 1976, ~, 2, pp.299-308, particularly l,pp.305-307: and by Begala et al, The Journal of Physical ZChemistry (1972), 76, 2, pp.25Z4-260 dealing with counterion ,Ibin~ing by polycarboxylates. The experimental evidence shows that the bindinZg of zinc to polymers is mostly ionic. Ionic 10 lbindinZg leads to either:
;, I a) chain bridging salts~ , Z
CH2 H20 H20, CH2 CH-COO- ~ CZllOC -CH Z
: CH2 H20 H20 ~ H2 15 b) intra chain salts~ ' , , 1.
, ,i 1 1, ~
! CH2 CH -COO H~O H20 ZZ
CH2 2n 2_ H20 f I !
;, CH-COO- H20 !
c) pendant half salts-Z
Cl H2 H20 H20 CH-COO-Zn -OH `
`' I / i !- CH2 H2 H20 ., Z
. . -- .
.. . .
= ., . . ~ .
d) chelate (ri~ structure with copolymers of vinylmethyl ether and maleic anhydride, since divalent cat~ons like zinc form a chelate with the ether oxygen and one carboxyl group~
j I ! , !
` I 0 - /+2- Jq ~
CH-~0 -2n 0-C-CH -or- IH C00 ~ n+~ H20 CH-0 ~ ~ 0-CH CH 0 / ¦ H~0 I; I I \ I I I ! \ ' 2'CH3 H20 C~ IH2 CH2 CH3 H20 i Accordingly, it is believed that the zinc-polymer complex iæ
ionically bound, but -the exact type of binding (which may also . lo exist as a mixture of above structures) has not been ascertained. !
.
~ ~ The following examples are given to illustrate this , ~ , invention further. In this application all proportions are by weight unless otherwise indicated, Exam~le 1 0.2gm zinechloride is dissolved in 15 ml water and ,added to a 4Y0 aqueous solution of the copolymer of maleic anhydride and methylvinyl ether with agitation and subsequently diluted to 200ml. A clear solution of the zinc-polymer complex , !
is obtained.
ExamPle 2 a) lOOg of an aqueous zinc oxide paste containing 0.5 zinc is prepared and added slowly with continuous stirring to 25 ml of a 1% aqueous solution of methylvinyl ether-maleic ilanhydride copolymer and subsequently diluted with 75 ml water.
iI The final solution has a pH of 5.5 and is slightly cloudy, The ratio of zinc to anionic polymer is 1~2.
b) 100 gm of an aqueous zinc oxide paste containing 0.25%
.l -13-l.
! l i ,, ~
A ,. . , _ ", _., ~, , - 10848~6 ; zinc is added to lOOgm of an aqueous solution containing 0.25%' methylvinyl ether-ma]eic anhydride copolymer with continuous agitation. The final solution has a pH of 6.~ a~ i8 turbid.
The ratio of zinc to anionic polymer is lt 1.
c) A final ~olution of zinc-polymer complex is prepared as above containin~ 0~25~o zinc and 1.0% anionic polymer, a ratio of 1:4, which has a pH of 3.5 and is clear, With the addition of about lOml. 3N ammonium hydroxide to said clear , solution, the pH is adjusted to 6.8 (pH in the oral cavity) and the solution retains its clarity.
This example clearly shows that the ratio of zinc salt to anionic polymer is dependant on the solubility of the i~
final zinc-polymer complex formed, maximum solubility being evidenced by a clear solution which is preferable although I ~
a slight cloudiness is also acceptable. I -ExamPle ~ j A zinc-polymer complex is prepared by mixing 50ml. of 0.05M aqueous solutions of the following zinc salts with 50ml of a 2% aqueuous solution of methylvinyl ether-maleic anhydride copolymer and the pH is adjusted to 5-6 with ammonium hydroxide. The ratio of zinc to polymer is ls 4.
a. zinc oxide which contains 80~34~o zinc and is water insoluble.
b. zinc chloride which contains 47~97/~o zinc and is water soluble.
c. zinc glycerophosphate which contains 27~77~o zinc and is soluble in water and insoluble in alcohol, d. zinc salicylate which contains 19.25~o zinc and is soluble in water and alcohol.
e. zinc alpha glucoheptonate which contains 19~7~o zinc and is water soluble.
., i , . . . .
,, . :
.1 ;, .j f. zinc propionate which contains 30.91~ zinc and is only 32~ soluble in water and 28J/o soluble in alcohol.
Ig. zinc salt of 8-hydroxyquinoline which contains 18.48~o zinc and is water insoluble.
l~h. zinc gluconate which contains 25~ zinc and is water soluble.
l¦i. zinc pyrophosphate which contains 42.91% zinc and is - I insoluble in water, but soluble in dilute mineral acids.
~ The final solutions containing the zinc-anionic polymer .~ li ; lcomplex were all clear except for the solutions containing zinc pyrophosphate which was cloudy and turbid, the zinc 8-hydroxyquinoline which was yellow and turbid and the zinc glycerophosphate which was cloudy and slightly turbid. The ` zinc propionate which was initially a cloudy precipitate ~became clear upon the addition of the anionic polymer.
' While particularly good results in terms of odor inhibition and other salutary effects in the oral cavity and on tooth surfaces, have thus far been obtained by applying simply the aqueous solutions or dispersions of the zinc-polymer complex, it will be understood that it is within the broader aspect of the invention to incorporate said complex into oral compositions generally, such as clear or cloudy mouth rinses and transparant or opaque toothpastes, troches, chewing gum, tablet or powder containing a dental vehicle.
; Likewise, the complex may be formed in situ, during the ?
preparation of said oral compositions or even on dilution in ,, the mouth; or the zinc compound and the anionic polymer may imerely act cooperatively within said oral cavity and not form :, ; a detectable complex.
,. -15- ~
, . , ._ ~
108484~;
! The vehicle, often referred to as a dental vehicle contains liquids and solids. In general, the liquid compri8es ` !Iwater and/or a humectant such as glycerine, sorbitol, propylene glycol or polyethylene glycol 400 including suitable mixtures ~Ithereof. It is usually advantageous to use a mixture of both ! water and one or two humectants. The total liquid content is ;; ~
Igenerally about 20-90 percent by weight of the vehicle. In ¦transparent and translucent vehicles, the liquid content of the toothpaste may be about 20-90 percent by weight, while in opaque lo ~vehicles the total liquid content is usually about 20-50 percent~
by weight. The preferred humectants are glycerine and sorbitol.
Typically clear, that is transparent or translucent, vehicle contains 0-80 percent by weight of glycerine, about 20-80 percent by weight of sorbitol and about 20-80 percent by 'Iweight of water. Opaque vehicles typically contain about 15-35 percent by weight of glycerine and about 10-30 percent by weight of water.
The solid portion of-~e vehicle is a gelling agent.
'In the instant invention the gelling agent includes alkali , metal carboxymethyl cellulose in amount of at least about 0.25 percent by weight of the vehicle. Additional gelling agents may also be present. Gelling agents which~ay be addi-tionally present include viscarin, gelatin, starch, glucose, sucrose, polyvinyl pyrollidone, polyvinyl alcohol, gum traga-canth, gum karaya, hydroxy propyl cellulose, methyl cellulose,carboxyethyl cellulose, sodium alginate. Laponite CP or SP, ` which are each synthetic inorganic complex silicate clays sold under trademark by Laporte Industries, Lt~d., and magnesium ,¦ aluminum silicate gel. The solid portion or gelling agent of
484~
oral composition effective in inhibiting mouth odor over a protracted period of time.
Still another object of this invention is to provide an oral com-position effective in inhibiting plaque, calculus, caries and periodontal disease.
It has been found, through radioisotope studies, that anionic polymers can be adsorbed onto oral surfaces. Accordingly, an effective method of controlling mouth odor entails the use of an oral composition comprising a zinc polymer salt or complex formed by combining zinc compounds with anionic polymers. The positively charged zinc ions can react with the poly-meric carboxyl, sulfonic or phosphonic acid groups of the anionic polymers to form zinc-polymer combinations. In the presence of excess acidic groups, the zinc-polymer combinations adsorb onto the oral surfaces such as the teeth and oral mucosa, thereby forming a reservoir of zinc ions capable of being gradually released with time into the oral environment.
According to the present invention, there is provided a non-astringent tasting oral composition capable of countering mouth odor, compris-ing effective amounts of a combination of a zinc compound and an anionic polymer containing carboxylic, sulfonic or phosphonic acid radicals. Said zinc-polymer combinations provide both a means of attachment to the oral cav-ity as well as form a reservoir of zinc ions which are gradually released over a protracted period of ~ime as an effective means to combat mouth odor, pla~ue, calculus, and periodontal disease. In addition, the zinc-polymer combinations decrease the high astringency which is characteristic of zinc ions, thereby leaving a more pleasant taste in the mouthO
It has been ascertained through equilibrium dialysis ...
.. ... .
:
... .
108484~
', , i ' studies against water that the zinc ions are bound tothe ianionic polymer and are slowly released with time as clearly indicated by the results in Table I, wherein 0. 025% zinc oxide llplus 2,',~ of a copolymer of vinyl methyl ether and maleic ~lanhydride having a molecular weight of 250~ 000 (Gantrez 119) I ,!was tested against zinc oxide per se.
1,l ,l Table I
Equilibrium Dial~sis Studies l Rate of Dissociation 10 , _ Coml~ound 10 Min 1 Hr 24 Hrs ~Zn 2 ~ Gantreztll9 * 0 0 53 ,zn+2 ~ H20 21 70 100 . ' ~
Ij j * 0. 025~o zinc oxide + 2~o Gantrez 119 ; pH adjusted to 6~5 with ** 0~ 025~ zinc oxide t lN HCl ; pH adjusted to 6 ~ 5 with 3N NH40H
I
The above table clearly shows that no zinc was detected in the dialysate (ou-tside membrane) after 10 minutes, and after 1 hour of dialysis; and only ~3~o zinc was found in the ', ,Idialysate after 24 hours dialysis. Whereas, in the absence of ,,the polymer, 21~ zinc was detected in the dialysate after ', ' '.only 10 minutes, 70~ zinc was found after only 1 hour and lOO~o .zinc was found in the dialysate after 24 hours dialysis. In '.'the presence of saliva salts, the zinc ions are bound to the ¦
'Ipolymer and are even more gradually released wi~h time, with "only 7~ zinc being detected in the dialysate after 24 AurS.
''t Trademark ., -4-., ~
"
,' ' 10848~6 , In contrast, in the absence of the polymer, thezinc is dialyzed ~out ~% after 10 minutes; 50% after 1 hour; and lOO~o after 24hours.
~l 'l'he anionic polymers are well known in the art. Prefer-ably, the polymer is one which is linear and water-soluble.
For example, it may be soluble in water, when in its sodium or ammonium salt form, at least to i;he extent of the concen- ¦
tration in which it is employed ( O. l~o to lO~o) . See for instance lithe anionic polymeric materials described in U.S. No. 2,984,639, lo 3,325,402, 3,429,963, the article on "Polyelectrolytes" in Vol. 10 of Encyclopedia of Polymer Science pages 781 ff, particularly pages 781, 782 and 784 listing various poly-electrolytes. The anionic polymers employed herein preferably ~ contain ionizable carboxyl, sulfonic or phosphonic groups. A
preferred type of polymers has its ionic substituents on a polymer chain which is hydrocarbon preferably aliphatic ~hydrocarbon (e.g. a vinyl polymer). Typical of such anionic polymers are copolymers of an unsaturated polybasic carboxylic lacid or anhydride thereof (preferably dibasic and having 4 carbon atoms per molecule) and of an olefin having 2 or more carbon atoms per molecule; polyolefin sulfonates; polyolefin phosphonates; and polyolefin phosphates, the olefin group -~
containing 2 or more carbon atoms. Suitable examples include~ !
' 1. A copolymer of maleic anhydride with ethylene, or 25 i styrene, or isobutylene, or polymethyl vinyl ether, or , polyethylvinyl ether, having recurring ~roups:
; ' X ff H---CH
¦! OOM COOM1 ' wherein ~ and r~!1 are individual~y hydrogen, sodium, potassium .~ -5-~, , I
__ ... ._._. ~, 'lor arnrnoniu~n and may be the same or different, and X is ethylene, styrene, isobutylene, methylvinyl ether, and ! ethylvinyl ether.
Il 2. A polyacrylic acid and polyacrylates thereof having 5 It recurring groups: ¦
¦~ _ CH------CH2 IH CH2 ¦I COO~ COOM
,~wherein M and ~1 have the same meaning as above.
Il 3. A polyitaconic acid and polyitaconates thereof 10 llhaving recurring groups: ~' ~H2 ff O~M
{~H2 OOM
, 1 ~'wherein M and ~1 have the same meaning as above.
ll 4. A polyolefin sulfonate having recurring groupss CH - CH
0=~=0 I OM
~,wherein M has the same meaning as above.
5, A polyvinyl phosphonate having recurring groups:
i ii MO-~=o . ' OMl !
~ j 6, A polyvinyl phosphate having recurring groups- i , ,, ~
' MO-P~O
~M 1 , _ . , .
1~3848~6 .
I
~Good results have been obtained with anionic polymers of very high molecular weight such as about 500~000 or 1,O00,000 as well as of relative]y low molecular weights of at least l,OO0 'land preferably 1,500 to 500,000. The anionic polymer consti-~tutes about 0.1 to 10~ by weight and preferably 0~5-1~5yo of the oral composition.
The zinc compounds that form the zinc-polymer combination by reaction or interaction with said anionic polymer may be any physiologically acceptable zinc salt including the water soluble and insoluble, organic and inorganic zinc salts.
Any zinc compound equivalent to 1.5 mFI/ml zinc may be mixed with the anionic polymer. Examples of suitable zinc compounds that may be employed includes ,'~zinc acetate zinc isovalerate 15~ 'zinc acetylacetonate zinc D-lactate zinc ammonium sulfate zinc DL-lactate zinc benzoate zinc laurate i r zinc bromide zinc hexafluorosilicate zinc beryllium orthosilicate zinc methacrylate zinc borate zinc molybdate 'zinc butylphthalate zinc naphthenate zinc butylxanthate zinc octoate ~' zinc caprylate zinc oleate ; zinc carbonate zinc orthophosphate zinc chloroanilate zinc phenolsulfonate ~ zinc chlorate zinc pyridine-2-thiol-1-oxide I zinc chromate zinc pyrophosphate , zinc citrate zinc resinate i zinc cyclohexanebutyrate zinc salicylate ~ -7-' i .
zinc chlori~ zinc sulfate zinc ~allate zinc nitrate zinc fluoride zinc selenide zinc alpha-glucoheptonate zinc stearate zinc gluconate zinc sulfanilate zinc glycerophosphate zinc tartrate zinc hydroxide zinc tellurate zinc ~-hydroxyquinoline zinc tungstate ,zinc 12-hydroxystearate zinc valerate 10 ~!zinc iodide zinc vanadate zinc acrylate zinc tribromosalicylanilide zinc oxide zinc ricinoleate ;zinc propionate '~Although the majority of ~e zinc salts might have limited solubility in water, the presence of the anionic polymer does increase the solubility of the combinction. Zinc oxide or zinc ~propionate, for example, are insoluble in water but in the presence of adequate amounts of the anionic polymer they are Ijsolubilized. The pH thereof can be adjusted to ~.5 to 7.0 `with dilute NH40H and the clarity of the solutions are retained.
~,any insoluble zinc salts are rendered soluble when combined with the anionic polymers, thereby providing a means of following the interaction or reaction between zinc and the anionic polymer. The zinc compound constitutes about .01-5%
~5 and preferably .025-1~ by weight of the oral composition.
The solubility of the zinc-polymer combination appears to be a factor in the activity against odor formation. Soluble conlbinations of anionic polymer and zinc salt aEe very effective in inhibiting odor formation, whereas insoluble zinc-!~olymer combinations are less effective in reducing odor Ii i , . _ formation. Soluble combinations of the anionic polymer withzinc oxide, or zinc propionate are very effective in inhibiting VSC (volatile sulfur compoun~),whereas the insoluble zinc-polymer combinations such as polymer ~ zinc pyrophosphate, zinc ~lycerophosphate, or zinc, 8-OH quinoline were ineffective or only slightly effective.
Another factor which influences the efficacy of the zinc-poly~er comb~ion as an odor-inhibitor is the counterion in the original zinc compound. The zinc gluconate, and zinc alpha-glucoheptonate polymer combinations are soluble but substantially inactive in reducin~ mouth odor. The zinc salicylate-~olymer combinations are possibly effective a~ainst , ..
periodontal disease because of the anti-inflammatory properties of the salicylate counterion in addition to the benefit from ' 15 the zinc ions of the suppression of mouth odor. I
Aqueous solutions and dispersions of various zinc compounds were tested in an in vitro system co~sting of whole ,human saliva, L-cysteine as substrate, and incubated for 3 , hours at 37C in an airtight container. After incubation, ~ithe headspace VSC (volatile sulfur compoun~)formation was ,,measured by an instrumental GC-flame photometric technique.
Since mouth odor has been attributed to the presence of ` volatile sulfur compounds such as hydrogen sulfide, methyl mercaptan and dimethyl sulfide resulting from putrefactive processes occuring in the oral cavity, aforesaid in vitro test provide results comparable to in vivo sensory evaluations.
The results, as set forth in ~able II, show excellent VSC
inhibition for the zinc oxide, zinc chloride and zinc propionate combinations with the anionic polymer. Zinc chloride plus water was used as the control compound.
!
.
.
~084846 Table II
Com~ound *~O VSC Inhibition Zinc oxide + G-1191 (soluble) 52 ¦
;IZinc chloride + G-119 (soluble) 36 5 IZinc propionate + G-ll9 (soluble) 53 Zinc gluconate + G-119 (soluble) f 15 IlZinc alpha-glucoheptonate + G-119 (soluble) 15 : Zinc pyrophosphate (insoluble) f 12 .Zinc glycerophosphate + G-ll9 (slightly soluble) 13 lo iZinc 8-OH quinoline + G-119 (slightly soluble) 24 ,l Zinc salicylate + G-119 (soluble) - 17 .
~ Zinc chloride + H20 54 . I
' ' ', ~ Zinc equivalent to 1.6 mg/ml: G-ll~ - 0.1%; pH between 6.5 to !~ 7 ~ ~
- 15 , 1 G-ll9 is the anionic polymer defined in Table I
`. f indicative of promotion of odor formation as opposed to : inhibition .
In addition to the efficacy of the zinc-polymer combina-tions as a mouth odor inhibitor, the taste thereof is distinctly ;different from, and an improvement over, that of zinc chloride as evidenced by a testing program wherein a panel of five persons tasted two samples, via a mouthrinse, containing , _, _ .
equivalent concentrations of zinc ions; one sample containing t Izinc chloride/poly~er combination and the other containing zinc chloride/water plus 0.2% flavor(both at a pH between 5.5-5.~). The participants agreed, without exception, that 5 the two samples were distinctly different and that the zinc 'Ichloride-polymer sample had very little of the astringent, jmetallic taste characteristic of zinc ions. These results show that the presence of the polymer improves the taste f ! ;i zinc-containing solutions by eliminating the astringent taste lO jland the numbing of the tongue attributable to the zinc ions.
~Thus, it is apparent that the zinc-polymer combinations are ;particularly useful in formulations where the taste of zinc creates a disadvantage.
Aqueous dispersions or solutions of zinc-polymer com-15 bination may be produced by adding a zinc salt in the form of ~a dilute solution, a paste or in the dry state, to a dilute solution of anionic polymer, and stopping the addition before the amount of zinc salt is such as to form a precipitate or gel. With good agitation and careful addition not to exceed 20 the amount of maximum solubility of the zinc-polymer complex, a clear solution or dispersion is obtained. This phenonema 'is clearly indicated in Example 2. The anionic polymer solution is preferable adjusted to a pH of about 5,5 with ~iammonium hydroxide or other suitable base prior to the addition 25 of the zinc salt. The pH of the final zinc polymer salt solution is about 4.5-6.o. For example, a suitable zinc polymer salt or complex is formed by adding 0.050M of a zinc salt to 500 ml of a 2~o solution of a copolymer of methylvinyl ether and maleic anhydride, (adjusted to a pH of 5,5 with 3N
30 ammonium hydroxide) and mixing well. The final solution or ., I
. . .
' 1084846 , '.
! disZpersi.on of the zine-anionic polymer complex preferably has a pH of abou-t 4.5-6.o. lt is believed th~t the ionized ~carboxyl groups react or interact with the zinc ion to form a zinc-polymer salt or complex. See the article by Crisp et lal, J Dent Res March-April 1976, ~, 2, pp.299-308, particularly l,pp.305-307: and by Begala et al, The Journal of Physical ZChemistry (1972), 76, 2, pp.25Z4-260 dealing with counterion ,Ibin~ing by polycarboxylates. The experimental evidence shows that the bindinZg of zinc to polymers is mostly ionic. Ionic 10 lbindinZg leads to either:
;, I a) chain bridging salts~ , Z
CH2 H20 H20, CH2 CH-COO- ~ CZllOC -CH Z
: CH2 H20 H20 ~ H2 15 b) intra chain salts~ ' , , 1.
, ,i 1 1, ~
! CH2 CH -COO H~O H20 ZZ
CH2 2n 2_ H20 f I !
;, CH-COO- H20 !
c) pendant half salts-Z
Cl H2 H20 H20 CH-COO-Zn -OH `
`' I / i !- CH2 H2 H20 ., Z
. . -- .
.. . .
= ., . . ~ .
d) chelate (ri~ structure with copolymers of vinylmethyl ether and maleic anhydride, since divalent cat~ons like zinc form a chelate with the ether oxygen and one carboxyl group~
j I ! , !
` I 0 - /+2- Jq ~
CH-~0 -2n 0-C-CH -or- IH C00 ~ n+~ H20 CH-0 ~ ~ 0-CH CH 0 / ¦ H~0 I; I I \ I I I ! \ ' 2'CH3 H20 C~ IH2 CH2 CH3 H20 i Accordingly, it is believed that the zinc-polymer complex iæ
ionically bound, but -the exact type of binding (which may also . lo exist as a mixture of above structures) has not been ascertained. !
.
~ ~ The following examples are given to illustrate this , ~ , invention further. In this application all proportions are by weight unless otherwise indicated, Exam~le 1 0.2gm zinechloride is dissolved in 15 ml water and ,added to a 4Y0 aqueous solution of the copolymer of maleic anhydride and methylvinyl ether with agitation and subsequently diluted to 200ml. A clear solution of the zinc-polymer complex , !
is obtained.
ExamPle 2 a) lOOg of an aqueous zinc oxide paste containing 0.5 zinc is prepared and added slowly with continuous stirring to 25 ml of a 1% aqueous solution of methylvinyl ether-maleic ilanhydride copolymer and subsequently diluted with 75 ml water.
iI The final solution has a pH of 5.5 and is slightly cloudy, The ratio of zinc to anionic polymer is 1~2.
b) 100 gm of an aqueous zinc oxide paste containing 0.25%
.l -13-l.
! l i ,, ~
A ,. . , _ ", _., ~, , - 10848~6 ; zinc is added to lOOgm of an aqueous solution containing 0.25%' methylvinyl ether-ma]eic anhydride copolymer with continuous agitation. The final solution has a pH of 6.~ a~ i8 turbid.
The ratio of zinc to anionic polymer is lt 1.
c) A final ~olution of zinc-polymer complex is prepared as above containin~ 0~25~o zinc and 1.0% anionic polymer, a ratio of 1:4, which has a pH of 3.5 and is clear, With the addition of about lOml. 3N ammonium hydroxide to said clear , solution, the pH is adjusted to 6.8 (pH in the oral cavity) and the solution retains its clarity.
This example clearly shows that the ratio of zinc salt to anionic polymer is dependant on the solubility of the i~
final zinc-polymer complex formed, maximum solubility being evidenced by a clear solution which is preferable although I ~
a slight cloudiness is also acceptable. I -ExamPle ~ j A zinc-polymer complex is prepared by mixing 50ml. of 0.05M aqueous solutions of the following zinc salts with 50ml of a 2% aqueuous solution of methylvinyl ether-maleic anhydride copolymer and the pH is adjusted to 5-6 with ammonium hydroxide. The ratio of zinc to polymer is ls 4.
a. zinc oxide which contains 80~34~o zinc and is water insoluble.
b. zinc chloride which contains 47~97/~o zinc and is water soluble.
c. zinc glycerophosphate which contains 27~77~o zinc and is soluble in water and insoluble in alcohol, d. zinc salicylate which contains 19.25~o zinc and is soluble in water and alcohol.
e. zinc alpha glucoheptonate which contains 19~7~o zinc and is water soluble.
., i , . . . .
,, . :
.1 ;, .j f. zinc propionate which contains 30.91~ zinc and is only 32~ soluble in water and 28J/o soluble in alcohol.
Ig. zinc salt of 8-hydroxyquinoline which contains 18.48~o zinc and is water insoluble.
l~h. zinc gluconate which contains 25~ zinc and is water soluble.
l¦i. zinc pyrophosphate which contains 42.91% zinc and is - I insoluble in water, but soluble in dilute mineral acids.
~ The final solutions containing the zinc-anionic polymer .~ li ; lcomplex were all clear except for the solutions containing zinc pyrophosphate which was cloudy and turbid, the zinc 8-hydroxyquinoline which was yellow and turbid and the zinc glycerophosphate which was cloudy and slightly turbid. The ` zinc propionate which was initially a cloudy precipitate ~became clear upon the addition of the anionic polymer.
' While particularly good results in terms of odor inhibition and other salutary effects in the oral cavity and on tooth surfaces, have thus far been obtained by applying simply the aqueous solutions or dispersions of the zinc-polymer complex, it will be understood that it is within the broader aspect of the invention to incorporate said complex into oral compositions generally, such as clear or cloudy mouth rinses and transparant or opaque toothpastes, troches, chewing gum, tablet or powder containing a dental vehicle.
; Likewise, the complex may be formed in situ, during the ?
preparation of said oral compositions or even on dilution in ,, the mouth; or the zinc compound and the anionic polymer may imerely act cooperatively within said oral cavity and not form :, ; a detectable complex.
,. -15- ~
, . , ._ ~
108484~;
! The vehicle, often referred to as a dental vehicle contains liquids and solids. In general, the liquid compri8es ` !Iwater and/or a humectant such as glycerine, sorbitol, propylene glycol or polyethylene glycol 400 including suitable mixtures ~Ithereof. It is usually advantageous to use a mixture of both ! water and one or two humectants. The total liquid content is ;; ~
Igenerally about 20-90 percent by weight of the vehicle. In ¦transparent and translucent vehicles, the liquid content of the toothpaste may be about 20-90 percent by weight, while in opaque lo ~vehicles the total liquid content is usually about 20-50 percent~
by weight. The preferred humectants are glycerine and sorbitol.
Typically clear, that is transparent or translucent, vehicle contains 0-80 percent by weight of glycerine, about 20-80 percent by weight of sorbitol and about 20-80 percent by 'Iweight of water. Opaque vehicles typically contain about 15-35 percent by weight of glycerine and about 10-30 percent by weight of water.
The solid portion of-~e vehicle is a gelling agent.
'In the instant invention the gelling agent includes alkali , metal carboxymethyl cellulose in amount of at least about 0.25 percent by weight of the vehicle. Additional gelling agents may also be present. Gelling agents which~ay be addi-tionally present include viscarin, gelatin, starch, glucose, sucrose, polyvinyl pyrollidone, polyvinyl alcohol, gum traga-canth, gum karaya, hydroxy propyl cellulose, methyl cellulose,carboxyethyl cellulose, sodium alginate. Laponite CP or SP, ` which are each synthetic inorganic complex silicate clays sold under trademark by Laporte Industries, Lt~d., and magnesium ,¦ aluminum silicate gel. The solid portion or gelling agent of
3 the vehicle is typically present in amount of about 0.25-lO
,' I
_ __ _ !
~0~4846 percent by weight of the toothpaste and preferably about 0.5-8 percent by weight. Alkali met~l carboxymethyl ~ellulose includes the lithium, sodium and potassium salts.
' Any suitable substantialy water-insoluble polishing 'lagent may be added to the gel vehicle. There i8 a relatively large number of such m~rials known in the art. Representative Imaterials include, for example, dicalcium phosphate, tricalcium ,phosphate, insoluble sodium metaphosphate, aluminum hydroxide, magnesium carbonate, calcium carbonate, calcium pyrophosphate, 'calcium sulfate, bentonite, etc., including suitable mixtures thereof. It is preferred to use the water-insoluble phosphate sodium metaphosphate and/or a calcium phosphate, such as dicalcium phosphate dihydrate. In general, these polishing ;agents will comprise a major proportion by weight of the solid ingredients. The polishing agent content is variable, but will 'generally be up to about 75 percent by weight of the total lcomposition~ generally about 20-75 percent; although, as indicated below, even lower amounts of polishing agent can be employed.
, Any suitable surface-active or detersive material may be iincorporated in the gel vehicle. Such compatible materials are desirable to provide additional detersive, foaming and antibacterial properties dependngupon the specific type of surface-active material and are selected similarly. These deter-!~gents are water-soluble organic compounds usually, and may be lanionic, nonionic, or cationic in structure. It is preferred to use the water-soluble non-soap or synthetic organic detergents usually. Suitable detersive materials are known and include, for example, the water-soluble salts of higher fatty acid mono-Iglyceride monosulfate detergent (e.c., sodium coconut fatty acid monoglyceride monosulfate), higher alkyl sulfates(e.g., sodium 1~ 1 . . ~
`' 10~4846 . I
l lauryl sulfate), alkyl aryl sulfonate (e.g., sodium dodecyl ll benzene sulfonate), higher fatty acid esters of 1,2-dihydroxy-I propane~ulfonate) and the like.
'!
The various surface-active materials may be used in any suitable amount, generally from about 0.05 to about 10 percent il by weight, and preferably from about 0.5 to 5 percent by weight Ij of the dentifrice composition.
It is a further embodiment of the present invention to 1, use the substantially saturated higher aliphatic acyl amides lo ll of lower aliphatic amino carboxylic acid compounds, such as ,I those llaving 12 to 16 carbons in the acyl radical, and as more particularly described in U.S. Patent No, 2,689,170 issued September 14, 1954. The amino acid portion is derived generally , from the lower aliphatic saturated monoamino carboxylic acids 1 having about 2 to 6 carbons, usually the monocarboxylic acid compounds. Suitable compounds are the fatty acid amides of , glycine, sarcosine, alanine, 3-aminopropanoic acid and valine having about 12 to 16 carbo~ in the acyl group. It is preferred Ii to use the N-lauroyl myristoyl and palmitoyl sarcoside compounds, 20 fi however, for optimum effects.
The amide compounds may be employed in the form of the 1, free acid or preferably as the water-soluble salts thereof, ' such as the alkali metal, ammonium, amine and alkylolamine salts. ¦
I! Specific examples thereof are sodium and potassium N-lauroyl, 25 1' myristoyl and palmitoyl sarcosides, ammonium and ethanolamine, N-lauroyl sarcoside, N-lauroyl sarcosine, and sodium N-lauroyl glycine and alanine. For convenience herein, reference to "amino carboxylic acid compound", "sarcoside", and the like refers to such compounds having a free carboxylic group or the water-soluble carboxylate salts.
iO84846 Various other matorials may be incorporated in the vehicles I
of this invention. ~xamt)les thereof are preservatives, silicones, !
chlorophyll compounds, ammoniated materials such as urea, I diammonium phosphate and mixtures thereof, materials which can increase contrast with the particles, such as ¦titanium dioxide and other constituents. These adjuvants are incorporated in the instant compositions in amounts which do not i,substantially adversely affect the properties and characteristics suitably selected and used in proper amount depending upon the , particular type of preparation involved.
~! Antibacterial agents may also be employed in the gelled vehicles of the instant invention. Typical antibacterial agents include:
N1-(4-chlorobenzyl)-N5-(2,4-dichlorobenzyl) biguanide;
15 ;l p-chlorophenyl biguanide;
,' I
_ __ _ !
~0~4846 percent by weight of the toothpaste and preferably about 0.5-8 percent by weight. Alkali met~l carboxymethyl ~ellulose includes the lithium, sodium and potassium salts.
' Any suitable substantialy water-insoluble polishing 'lagent may be added to the gel vehicle. There i8 a relatively large number of such m~rials known in the art. Representative Imaterials include, for example, dicalcium phosphate, tricalcium ,phosphate, insoluble sodium metaphosphate, aluminum hydroxide, magnesium carbonate, calcium carbonate, calcium pyrophosphate, 'calcium sulfate, bentonite, etc., including suitable mixtures thereof. It is preferred to use the water-insoluble phosphate sodium metaphosphate and/or a calcium phosphate, such as dicalcium phosphate dihydrate. In general, these polishing ;agents will comprise a major proportion by weight of the solid ingredients. The polishing agent content is variable, but will 'generally be up to about 75 percent by weight of the total lcomposition~ generally about 20-75 percent; although, as indicated below, even lower amounts of polishing agent can be employed.
, Any suitable surface-active or detersive material may be iincorporated in the gel vehicle. Such compatible materials are desirable to provide additional detersive, foaming and antibacterial properties dependngupon the specific type of surface-active material and are selected similarly. These deter-!~gents are water-soluble organic compounds usually, and may be lanionic, nonionic, or cationic in structure. It is preferred to use the water-soluble non-soap or synthetic organic detergents usually. Suitable detersive materials are known and include, for example, the water-soluble salts of higher fatty acid mono-Iglyceride monosulfate detergent (e.c., sodium coconut fatty acid monoglyceride monosulfate), higher alkyl sulfates(e.g., sodium 1~ 1 . . ~
`' 10~4846 . I
l lauryl sulfate), alkyl aryl sulfonate (e.g., sodium dodecyl ll benzene sulfonate), higher fatty acid esters of 1,2-dihydroxy-I propane~ulfonate) and the like.
'!
The various surface-active materials may be used in any suitable amount, generally from about 0.05 to about 10 percent il by weight, and preferably from about 0.5 to 5 percent by weight Ij of the dentifrice composition.
It is a further embodiment of the present invention to 1, use the substantially saturated higher aliphatic acyl amides lo ll of lower aliphatic amino carboxylic acid compounds, such as ,I those llaving 12 to 16 carbons in the acyl radical, and as more particularly described in U.S. Patent No, 2,689,170 issued September 14, 1954. The amino acid portion is derived generally , from the lower aliphatic saturated monoamino carboxylic acids 1 having about 2 to 6 carbons, usually the monocarboxylic acid compounds. Suitable compounds are the fatty acid amides of , glycine, sarcosine, alanine, 3-aminopropanoic acid and valine having about 12 to 16 carbo~ in the acyl group. It is preferred Ii to use the N-lauroyl myristoyl and palmitoyl sarcoside compounds, 20 fi however, for optimum effects.
The amide compounds may be employed in the form of the 1, free acid or preferably as the water-soluble salts thereof, ' such as the alkali metal, ammonium, amine and alkylolamine salts. ¦
I! Specific examples thereof are sodium and potassium N-lauroyl, 25 1' myristoyl and palmitoyl sarcosides, ammonium and ethanolamine, N-lauroyl sarcoside, N-lauroyl sarcosine, and sodium N-lauroyl glycine and alanine. For convenience herein, reference to "amino carboxylic acid compound", "sarcoside", and the like refers to such compounds having a free carboxylic group or the water-soluble carboxylate salts.
iO84846 Various other matorials may be incorporated in the vehicles I
of this invention. ~xamt)les thereof are preservatives, silicones, !
chlorophyll compounds, ammoniated materials such as urea, I diammonium phosphate and mixtures thereof, materials which can increase contrast with the particles, such as ¦titanium dioxide and other constituents. These adjuvants are incorporated in the instant compositions in amounts which do not i,substantially adversely affect the properties and characteristics suitably selected and used in proper amount depending upon the , particular type of preparation involved.
~! Antibacterial agents may also be employed in the gelled vehicles of the instant invention. Typical antibacterial agents include:
N1-(4-chlorobenzyl)-N5-(2,4-dichlorobenzyl) biguanide;
15 ;l p-chlorophenyl biguanide;
4-chlorobenzhydryl biguanide;
4-chlorobenzhydrylguanylurea;
N-3-lauroxypropyl-N-p-chlorobenzylbiguanide: !
, 1,6-di-p-chlorophenylbiguanide hexane;
20 ~ 1-(lauryldimethylammonium)-8-(p-chlorobenzyldimethyl-ammonium) octane dichloride;
4-chlorobenzhydrylguanylurea;
N-3-lauroxypropyl-N-p-chlorobenzylbiguanide: !
, 1,6-di-p-chlorophenylbiguanide hexane;
20 ~ 1-(lauryldimethylammonium)-8-(p-chlorobenzyldimethyl-ammonium) octane dichloride;
5,6-dichloro-2-guanidinobenzimidazole;
N1-p-chlorophenyl-N5-laurylbiguanide;
5-amino-1,3-bis(2-ethy~exyl)-3-methylhexahydro pyrimidines " and their non-toxic acid addition salts.
The antibacterial agent, when present, is employed in amounts of about 0.1-5 percent by weight, preferably about '' 0.05-5 percent.
' Any suitable flavoring or sweetening matèrials may be employed in formulating a flavor for the compositions of the ..
. - 1 9 -, i - ~ 1084846 present invention. ~xamples of suitable flavoring constituents ,include the flavoring oils, etc., oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, ,cinnamon, lemon and orange, as well as sodium methylsalicylate.
~ISuitable sweetening agents include sucrose, lactose, maltose, rbitol~ sodium cyclamate and saccharine. Suitably, flavor land sweetenin~ agent may together comprise from about 0,01 to 5 ,percent or more of the compositions of the instant invention.
~ A fluorine-containing compound having a beneficial effect llon the care and hygiene of the oral cavity, e.g., diminution of lenamel solubility in acid and protection of the teeth against decay may also be incorporated in the gelled vehicle. Exam~es thereof include sodium fluoride, stannous fluoride, potassium j'fluoride, potassium stannous fluoride (SnF2-KF), sodium hexa-,fluorostannate, stannous chlorofluoride, sodium fluorozirconate,~and sodium monofluorophosphate. These materials, which dis-associate or release fluorine-containing ions in water, suitably ~'may be present in an effective but non-toxic amount, usually ! ~ .
within the range of about 0.01 to 1 percent by weight of the water-soluble fluorine content thereof.
The oral preparation may also be a liquid such as mouth rinse which typically contains 20-99% by weight of an aqueous ~i ~lower aliphatic alcohol, preferably h~ving about 1-30% by weight alcohol such as ethanol, n-propyl, or isopropyl alcohol.
'' ~
,. I
Such oral preparations are typically applied by brushing the teeth or rinsing the oral cavity for 30-90 seconds at least once daily. Typical oral preparations of the invention which "
!
.
... . . ...
:, 1084846 ~can be applied in this manner are set forth below.
" ~xample 4 Preparation of Zinc-Polymer Mouthrinse ! Total volume = 1 liter 5 tlSolution A On mixing with B
(Mouthrinse concentra~e) ~ (gms/100 ml) Final conc:
Ethyl alcohol------ 20 10 Pluronic~F-108*---- 8 4 1 Flavor------------- 0.4 0.2 10 ~' ' Glycerin----------- 20 10 Saccharin---------- O. o6 o . o3 ll 0.1~ FD & C Color-- o.6 0.3 Deionized water q.s. 100.0 * A polyalkene oxide block polymer ,Solution B
(Zinc-Polymer Complex) A 2~ polymer solution is prepared by adding methyl vinyl etherl-maleic anhydride copolymer (Gantrez) to 500 ml of water (pre-heated ~to 90C) with continuous stirring until a clear solution is ob-"tained. The polymer solution is cooled to room temperature and the '`pH is adjusted to 5.5 with addition of 3N ammonium hydroxide. Thenl ,,0.05 M of zinc oxide salt is added with stirring. The mixture is a, ,clear solution.
, 500 ml of solution A is added to 500 ml of solution B with ~continuous stirring (e.g. magnetic stirrer). The pH Or the mixture~
is between 4 and 6, and is a clear mouth rinse. The final concen-ttration of zinc salt in the mouthrinse is 0.025 M and of polymer is 1~.
, Equilibrium dialysis studies showed that the zinc-polymer complex in a typical mouth rinse formulation retains its identity in the presence of saliva salts and ex~ibits a slow !
, t Trademark .
,; _ '` I
rate of dissociation. After 10 minutes, 3% dissociation was I! noted; after 1 hour, 5% dissociation occured; and after 24 hours, 12% ~issociation was measured. The slow release of the j zinc ions and the increased retention of the zinc in the oral cavity enhance the effectiveness of instant oral compositions ~containing the zinc-polymer complex against mouth odor, plaque, jgingivitis and other oral disorders.
Example 5 Mouthwash o ~1 %
Ethyl alcohol 15.0 Non-ionic detergent (Pluronic F-108)1 4.0 I Flavor Q.2 i~ I
15 !i Glycerin 10.0 Saccharin -3 j FD~C color (0.1%) 0-3 J' Anionic polymer (Gantrez~119)2 1.0 1~ Zinc chloride 0. 025 20 !i Water q.s. lOOml.
1 A polyalkene oxide block polymer J, i 2 Copolymer of maleic anhydride and methylvinyl ether having a malecular weight of 250~ 000~
' The zinc chloride powder is added to a 2~o aqueous solution ,f the anionic polymer and stirred until dissolved and the pH
"is adjusted to 5 ~ 5 with ammonium hydroxide and then the mouth rinse concentrate containing the remaining ingredients is added to the zinc-polymer solution in accordance with the procedure of xam ~) l e ~ -t Trademark ;
__ . . .. . _ ._ ..... . ~ ., _,, In vitro VSC Inhibition tests on thi~ mouthrinse in the presence of saliva gave the following resultsl ., I
! Table IlI
C Inhibition ~ Sample inc~bha~Son incu~at~
5 'I zinc chloride mouthrinse 72 50 zinc chloride-polymer rinse 72 80 'rhese results clearly show the long range effectiveness of the zinc-polymer complex as a mouth odor inhibitor.
.
. Example 6 .
Dental Cream ,1 ~o '~ Anionic polymer of Example 1 1.0 " Zinc chloride 0.025 ,~ Nonionic detergent* 1.00 ~.
15 ,! Glycerine 22.00 Sodium pyrophosphate 0.25 Car~oxymethyl cellulose 0.85 Sodium saccharin 0.20 1, Sodium benzoate 0.50 20 ' Calcium carbonate (precipitated) 5.00 Dicalcium phosphate dihydrate 46.75 ~`lavor 0.80 Water q.s.
. *Tweent80-Polyoxyethylene (20 moles ethylene oxide) sorbitan ' monooleate-t Trademark , !
,~ . . . .
,, ~ . .. ~ P
i 1084846 :
The zinc-polymer complex is prepared in accordance with ¦ the procedure of ~xample 4. The remaining ingredients are ,`admixed with agitation to form a base paste, which is then ~,mixed with the zinc-polymer complex, using either equal 5 ,volumes or weights of the base pasteana the preformed zinc- ¦
~ polymer complex.
jl An effective amount, e.g., about . 01-5~o zinc compound ~land 0.1 to lO~o anionic polymer may also be incorporated in an I inert carrier or dissolved in a suitable vehicle in the formu- ¦
lo ¦'lation of chewing gums and lozenges. Similarly, the zinc-~polymer complex may also be incorporated into a mouth spray.
A typical lozenge formula contains the following ingedients, in ~¦
percent by weight, based on the weight of the total formulation~ ¦
i 75~o to 98~o Sugar i' 5 l l~o to 20% Corn Syrup .1~ to l~o Flavor oil 0% to .03~0 Colorant(s) i .1% to 5~o Tableting Lubricant 1, .2% to 2% Water 20 ll .1% to lO~o Anionic polymer .01v~o to 5% Zn compound Sugarless pressed candy may also be formulated to include the complex ~ this invention. For products of this type, which ,'usually contain powdered sorbitol instead of sugar, synthetic ' sweeteners are mixed with the powdered sorbitol and flavor(s), i colorant(s) and a tablet lubricant are then added. The formula 'lis introduced into a tablet machine to shape the final product. I
A typical sugarless pressed candy contains the~following jl~ingredients~ in percent byweight, based on the weight of the , -24-. i '' 10848~16 ;'tota~. formulation: ' 98% to 99~ 5;Yo Sorbitol ,, .1% to . 9,~'o Flavor(s) 1~ o~r to . 02,~o Synthetic Sweeteners 5 ll oylO to .03% Colorant(s) . 055b to l~/o Tableting Lubricant ,l Obviously many variations of the above described procedures . may, be used to prepare pre~sed candies.
~ A typical chewing gum may contain the following ingredients, !
~! in percent by weight based on the weight of the total gum formu- j ,~ lation:
_n~redients Wei~ht Percent ', , Gum Base From about loYo to about 40% ~1 .l, Sucrose From about 50yo to about 75~o ~5 Corn Syrup or Glucose From about lO;~o to about 205~o Flavor Material From about 0.4~ to about 5%
, Anionic polymer From about .1% to about lO~Yo Zn compound F~om about ~Ol:~o to about 5%
~., An alternate chewing gum formulation is as followss 20 i, ~ Wei~ht Percent Gum Base From about lOY~o to about 50%
Binder From about 3C,~70 to about 10%
. ~
Filler (Sorbito~ Mannitolt ll or combinations thereof) From about 55% to about 80%
25 li Artificial Sweetener and, ! Flavor From about 0.1% to about 5~o ,! Anionic Polymer From about .15S to about 105~o '' Zn compound From about . 0150 to about 5~0 , In certain sugarless gums, there is used as thebinder ingredient 3 1l a solution of sorbitol in water containing from about 10% to , about ~0~, preferably frorn about 50'l~o to about 75yO by weight of t Trademark 1 10848g,~ 1 .
, I'sorbitol in H20. In others, there is used a gum acacia-in-¦'water system containing from about 30% to about 60~o~ preferablyfrom about 45~ to about 50~ by weight of gum acacia powder.
Il The above chewing gum formulations are exemplary only.
IlMany additional formulations are described in the prior art, and in carrying out this invention, such formulations can be ~employed. It is also pos~ble to prepare an acceptable chewing gum product containing a gum base, flavoring material and Zn-l~polymer complex according to the teaching of this invention.
1~ The ingredient referred to heretofore in the formulationssimply as "gum base" is susceptible to many variations. ln `general, a gum base is prepared by heating and blending various ingredients, such as natural gums, synthetic resins, waxes, plastici~ers, etc. in a manner well known in the art. Typical ; 15 , examples of the ingredients found in a chewing gum base are masticatory substances of vegetable origin, such as chicle, ; crown gum, nispero, rosidinha, jelutong, pendare, perillo, jniger gutta, tunu, etc.s masticatory substances of synthetic ~iorigin such as butadiene-styrene polymer, isobutylene-isoprene ~ copolymer, paraffin, petroleum wax, polyethylene, polyiso-'~butylene, polyvinylacetate, etc.; plasticizers such as lanolin,stearic acid, sodium stearate, potassium stearate, etc.
A preferred ingredient of instant composition is a non-ionic organic surfactant which provides increased prophylactic¦
laction, assists in achieving thorough and complete dispersion of instant compositions throughout the oral cavity and renders instant compositions more cosmetically acceptable. The non-ionic surfactant imparts to the composition de~ersive and foam-in~ properties, as well as maintains the flavoring materials 3 in solution (i.e., solubilizes flavor oils). In addition, the . , . , ~.
: - - -.. .
,Inon-ionics are completely compatible with the zinc-anionic ,',complex of this invention, thereby providing for a stable, lZ
,Ihomogeneous composition of superior mouth odor control.
The non-ionic organic surface active compounds which 5 11 are contemplated are commercially kno~n and comprise water-! soluble products which are derived from the condensation of an alkylene oxide or equivalent reactant and a reactive-hydrogen hydrophobe. The hydrophobic organic compounds may be aliphatic, llaromatic or heterocyclic, although the first two classes are lo ¦Zlpreferred. The preferred types of hydrophobes are higher Z
l aliphatic alcohols and alkyl phenols, although others may be - used such as carboxylic acids, carboxamides, sulphonamides, etc. The ethylene oxide condensates with ~,higher-alkyl phenols represent a preferred class of non-ionic 15 icompounds. Usually the hydrophobic moiety should contain at Z
`lleast about 6 carbon atoms, and preferably at least about 8 ! carbon atoms, and may contain as many as about 50 carbon atoms or more. The amount of alkylene oxide will vary considerably, ~depending upon the hydrophobe, but as a general guide and rule, 20 at least about 5 moles of alkylene oxide per mole of hydrophobe should be used. The upper limit of alkylene oxide will vary also, but no particular criticality can be ascribed thereto IAs much as 200 or more moles of alkylene oxide per mole of jhydrophobe may be employed. While ethylene oxide is the pre-25 ~ferred and predominating oxyalkylating reagent, other lower alkylene oxides such as propylene oxide, butylene oxide, and the like, may also be used or substituted in part for the ethylene oxide. Other non-ionic compounds whicn are suitable are the polyoxyalkylene ester~ of the organic acids such as ~ 3 i the higher fatty acids, the rosin acids, tall oil acids, acids ., '', ., , ~ ~Z
.,. i.
,ifrom petroleum oxidation products, etc. These esters will usually contain from about lO to about 22 carbon atoms in the lacid moiety and from about 12 to about 30 moles of ethylene 'oxide or its equivalent.
l~ Still other non-ionic surfactants are the alkylene oxide ~Icondensates with the higher fatty acid amides. The fatty acid 'Igroup will generally contain from about ~ to about 22 carbon ¦atoms and this will be condensed with about lO to about 50 I moles of ethylene oxide as the preferred illustration. The llcorrespondin~r carboxamides and sulphonamides may also be used as substantia1 equivalents.
S-till another class of non-ionic products are the oxyalky- ¦
lated higher aliphatic alcohols. The fatty alcohols should contain at least 6 carbon atoms, and preferably at least about l8 carbon atoms- The most preferred alcohols are lauryl, myri-styl, cetyl, stearyl and oleyl alcohols and the acid alcohols should be condensed with at least about 6 moles of ethylene oxide, and preferably about lO to 30 moles of ethylene oxide..
,A typical non-ionic product is oleyl alcohol condensed with 15 moles of ethylene oxide.
,' i The amount of non-ionic may generally be varied.from about 0 2-3 0~o by weight of the total formulation, depending 'lon the specific nature of the non-ionic utilized, as well as lon the amounts and nature of the oth~ringredients in the oral ¦ .-iformulation.
Although this invention has been described with referenceto specific examples, it will be apparent to one skilled in the art that various modifications may be made thereto which fall within its scope.
; _ _ ._ . , , ,.. ,, . . ... _ , . .. . _~,,
N1-p-chlorophenyl-N5-laurylbiguanide;
5-amino-1,3-bis(2-ethy~exyl)-3-methylhexahydro pyrimidines " and their non-toxic acid addition salts.
The antibacterial agent, when present, is employed in amounts of about 0.1-5 percent by weight, preferably about '' 0.05-5 percent.
' Any suitable flavoring or sweetening matèrials may be employed in formulating a flavor for the compositions of the ..
. - 1 9 -, i - ~ 1084846 present invention. ~xamples of suitable flavoring constituents ,include the flavoring oils, etc., oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, ,cinnamon, lemon and orange, as well as sodium methylsalicylate.
~ISuitable sweetening agents include sucrose, lactose, maltose, rbitol~ sodium cyclamate and saccharine. Suitably, flavor land sweetenin~ agent may together comprise from about 0,01 to 5 ,percent or more of the compositions of the instant invention.
~ A fluorine-containing compound having a beneficial effect llon the care and hygiene of the oral cavity, e.g., diminution of lenamel solubility in acid and protection of the teeth against decay may also be incorporated in the gelled vehicle. Exam~es thereof include sodium fluoride, stannous fluoride, potassium j'fluoride, potassium stannous fluoride (SnF2-KF), sodium hexa-,fluorostannate, stannous chlorofluoride, sodium fluorozirconate,~and sodium monofluorophosphate. These materials, which dis-associate or release fluorine-containing ions in water, suitably ~'may be present in an effective but non-toxic amount, usually ! ~ .
within the range of about 0.01 to 1 percent by weight of the water-soluble fluorine content thereof.
The oral preparation may also be a liquid such as mouth rinse which typically contains 20-99% by weight of an aqueous ~i ~lower aliphatic alcohol, preferably h~ving about 1-30% by weight alcohol such as ethanol, n-propyl, or isopropyl alcohol.
'' ~
,. I
Such oral preparations are typically applied by brushing the teeth or rinsing the oral cavity for 30-90 seconds at least once daily. Typical oral preparations of the invention which "
!
.
... . . ...
:, 1084846 ~can be applied in this manner are set forth below.
" ~xample 4 Preparation of Zinc-Polymer Mouthrinse ! Total volume = 1 liter 5 tlSolution A On mixing with B
(Mouthrinse concentra~e) ~ (gms/100 ml) Final conc:
Ethyl alcohol------ 20 10 Pluronic~F-108*---- 8 4 1 Flavor------------- 0.4 0.2 10 ~' ' Glycerin----------- 20 10 Saccharin---------- O. o6 o . o3 ll 0.1~ FD & C Color-- o.6 0.3 Deionized water q.s. 100.0 * A polyalkene oxide block polymer ,Solution B
(Zinc-Polymer Complex) A 2~ polymer solution is prepared by adding methyl vinyl etherl-maleic anhydride copolymer (Gantrez) to 500 ml of water (pre-heated ~to 90C) with continuous stirring until a clear solution is ob-"tained. The polymer solution is cooled to room temperature and the '`pH is adjusted to 5.5 with addition of 3N ammonium hydroxide. Thenl ,,0.05 M of zinc oxide salt is added with stirring. The mixture is a, ,clear solution.
, 500 ml of solution A is added to 500 ml of solution B with ~continuous stirring (e.g. magnetic stirrer). The pH Or the mixture~
is between 4 and 6, and is a clear mouth rinse. The final concen-ttration of zinc salt in the mouthrinse is 0.025 M and of polymer is 1~.
, Equilibrium dialysis studies showed that the zinc-polymer complex in a typical mouth rinse formulation retains its identity in the presence of saliva salts and ex~ibits a slow !
, t Trademark .
,; _ '` I
rate of dissociation. After 10 minutes, 3% dissociation was I! noted; after 1 hour, 5% dissociation occured; and after 24 hours, 12% ~issociation was measured. The slow release of the j zinc ions and the increased retention of the zinc in the oral cavity enhance the effectiveness of instant oral compositions ~containing the zinc-polymer complex against mouth odor, plaque, jgingivitis and other oral disorders.
Example 5 Mouthwash o ~1 %
Ethyl alcohol 15.0 Non-ionic detergent (Pluronic F-108)1 4.0 I Flavor Q.2 i~ I
15 !i Glycerin 10.0 Saccharin -3 j FD~C color (0.1%) 0-3 J' Anionic polymer (Gantrez~119)2 1.0 1~ Zinc chloride 0. 025 20 !i Water q.s. lOOml.
1 A polyalkene oxide block polymer J, i 2 Copolymer of maleic anhydride and methylvinyl ether having a malecular weight of 250~ 000~
' The zinc chloride powder is added to a 2~o aqueous solution ,f the anionic polymer and stirred until dissolved and the pH
"is adjusted to 5 ~ 5 with ammonium hydroxide and then the mouth rinse concentrate containing the remaining ingredients is added to the zinc-polymer solution in accordance with the procedure of xam ~) l e ~ -t Trademark ;
__ . . .. . _ ._ ..... . ~ ., _,, In vitro VSC Inhibition tests on thi~ mouthrinse in the presence of saliva gave the following resultsl ., I
! Table IlI
C Inhibition ~ Sample inc~bha~Son incu~at~
5 'I zinc chloride mouthrinse 72 50 zinc chloride-polymer rinse 72 80 'rhese results clearly show the long range effectiveness of the zinc-polymer complex as a mouth odor inhibitor.
.
. Example 6 .
Dental Cream ,1 ~o '~ Anionic polymer of Example 1 1.0 " Zinc chloride 0.025 ,~ Nonionic detergent* 1.00 ~.
15 ,! Glycerine 22.00 Sodium pyrophosphate 0.25 Car~oxymethyl cellulose 0.85 Sodium saccharin 0.20 1, Sodium benzoate 0.50 20 ' Calcium carbonate (precipitated) 5.00 Dicalcium phosphate dihydrate 46.75 ~`lavor 0.80 Water q.s.
. *Tweent80-Polyoxyethylene (20 moles ethylene oxide) sorbitan ' monooleate-t Trademark , !
,~ . . . .
,, ~ . .. ~ P
i 1084846 :
The zinc-polymer complex is prepared in accordance with ¦ the procedure of ~xample 4. The remaining ingredients are ,`admixed with agitation to form a base paste, which is then ~,mixed with the zinc-polymer complex, using either equal 5 ,volumes or weights of the base pasteana the preformed zinc- ¦
~ polymer complex.
jl An effective amount, e.g., about . 01-5~o zinc compound ~land 0.1 to lO~o anionic polymer may also be incorporated in an I inert carrier or dissolved in a suitable vehicle in the formu- ¦
lo ¦'lation of chewing gums and lozenges. Similarly, the zinc-~polymer complex may also be incorporated into a mouth spray.
A typical lozenge formula contains the following ingedients, in ~¦
percent by weight, based on the weight of the total formulation~ ¦
i 75~o to 98~o Sugar i' 5 l l~o to 20% Corn Syrup .1~ to l~o Flavor oil 0% to .03~0 Colorant(s) i .1% to 5~o Tableting Lubricant 1, .2% to 2% Water 20 ll .1% to lO~o Anionic polymer .01v~o to 5% Zn compound Sugarless pressed candy may also be formulated to include the complex ~ this invention. For products of this type, which ,'usually contain powdered sorbitol instead of sugar, synthetic ' sweeteners are mixed with the powdered sorbitol and flavor(s), i colorant(s) and a tablet lubricant are then added. The formula 'lis introduced into a tablet machine to shape the final product. I
A typical sugarless pressed candy contains the~following jl~ingredients~ in percent byweight, based on the weight of the , -24-. i '' 10848~16 ;'tota~. formulation: ' 98% to 99~ 5;Yo Sorbitol ,, .1% to . 9,~'o Flavor(s) 1~ o~r to . 02,~o Synthetic Sweeteners 5 ll oylO to .03% Colorant(s) . 055b to l~/o Tableting Lubricant ,l Obviously many variations of the above described procedures . may, be used to prepare pre~sed candies.
~ A typical chewing gum may contain the following ingredients, !
~! in percent by weight based on the weight of the total gum formu- j ,~ lation:
_n~redients Wei~ht Percent ', , Gum Base From about loYo to about 40% ~1 .l, Sucrose From about 50yo to about 75~o ~5 Corn Syrup or Glucose From about lO;~o to about 205~o Flavor Material From about 0.4~ to about 5%
, Anionic polymer From about .1% to about lO~Yo Zn compound F~om about ~Ol:~o to about 5%
~., An alternate chewing gum formulation is as followss 20 i, ~ Wei~ht Percent Gum Base From about lOY~o to about 50%
Binder From about 3C,~70 to about 10%
. ~
Filler (Sorbito~ Mannitolt ll or combinations thereof) From about 55% to about 80%
25 li Artificial Sweetener and, ! Flavor From about 0.1% to about 5~o ,! Anionic Polymer From about .15S to about 105~o '' Zn compound From about . 0150 to about 5~0 , In certain sugarless gums, there is used as thebinder ingredient 3 1l a solution of sorbitol in water containing from about 10% to , about ~0~, preferably frorn about 50'l~o to about 75yO by weight of t Trademark 1 10848g,~ 1 .
, I'sorbitol in H20. In others, there is used a gum acacia-in-¦'water system containing from about 30% to about 60~o~ preferablyfrom about 45~ to about 50~ by weight of gum acacia powder.
Il The above chewing gum formulations are exemplary only.
IlMany additional formulations are described in the prior art, and in carrying out this invention, such formulations can be ~employed. It is also pos~ble to prepare an acceptable chewing gum product containing a gum base, flavoring material and Zn-l~polymer complex according to the teaching of this invention.
1~ The ingredient referred to heretofore in the formulationssimply as "gum base" is susceptible to many variations. ln `general, a gum base is prepared by heating and blending various ingredients, such as natural gums, synthetic resins, waxes, plastici~ers, etc. in a manner well known in the art. Typical ; 15 , examples of the ingredients found in a chewing gum base are masticatory substances of vegetable origin, such as chicle, ; crown gum, nispero, rosidinha, jelutong, pendare, perillo, jniger gutta, tunu, etc.s masticatory substances of synthetic ~iorigin such as butadiene-styrene polymer, isobutylene-isoprene ~ copolymer, paraffin, petroleum wax, polyethylene, polyiso-'~butylene, polyvinylacetate, etc.; plasticizers such as lanolin,stearic acid, sodium stearate, potassium stearate, etc.
A preferred ingredient of instant composition is a non-ionic organic surfactant which provides increased prophylactic¦
laction, assists in achieving thorough and complete dispersion of instant compositions throughout the oral cavity and renders instant compositions more cosmetically acceptable. The non-ionic surfactant imparts to the composition de~ersive and foam-in~ properties, as well as maintains the flavoring materials 3 in solution (i.e., solubilizes flavor oils). In addition, the . , . , ~.
: - - -.. .
,Inon-ionics are completely compatible with the zinc-anionic ,',complex of this invention, thereby providing for a stable, lZ
,Ihomogeneous composition of superior mouth odor control.
The non-ionic organic surface active compounds which 5 11 are contemplated are commercially kno~n and comprise water-! soluble products which are derived from the condensation of an alkylene oxide or equivalent reactant and a reactive-hydrogen hydrophobe. The hydrophobic organic compounds may be aliphatic, llaromatic or heterocyclic, although the first two classes are lo ¦Zlpreferred. The preferred types of hydrophobes are higher Z
l aliphatic alcohols and alkyl phenols, although others may be - used such as carboxylic acids, carboxamides, sulphonamides, etc. The ethylene oxide condensates with ~,higher-alkyl phenols represent a preferred class of non-ionic 15 icompounds. Usually the hydrophobic moiety should contain at Z
`lleast about 6 carbon atoms, and preferably at least about 8 ! carbon atoms, and may contain as many as about 50 carbon atoms or more. The amount of alkylene oxide will vary considerably, ~depending upon the hydrophobe, but as a general guide and rule, 20 at least about 5 moles of alkylene oxide per mole of hydrophobe should be used. The upper limit of alkylene oxide will vary also, but no particular criticality can be ascribed thereto IAs much as 200 or more moles of alkylene oxide per mole of jhydrophobe may be employed. While ethylene oxide is the pre-25 ~ferred and predominating oxyalkylating reagent, other lower alkylene oxides such as propylene oxide, butylene oxide, and the like, may also be used or substituted in part for the ethylene oxide. Other non-ionic compounds whicn are suitable are the polyoxyalkylene ester~ of the organic acids such as ~ 3 i the higher fatty acids, the rosin acids, tall oil acids, acids ., '', ., , ~ ~Z
.,. i.
,ifrom petroleum oxidation products, etc. These esters will usually contain from about lO to about 22 carbon atoms in the lacid moiety and from about 12 to about 30 moles of ethylene 'oxide or its equivalent.
l~ Still other non-ionic surfactants are the alkylene oxide ~Icondensates with the higher fatty acid amides. The fatty acid 'Igroup will generally contain from about ~ to about 22 carbon ¦atoms and this will be condensed with about lO to about 50 I moles of ethylene oxide as the preferred illustration. The llcorrespondin~r carboxamides and sulphonamides may also be used as substantia1 equivalents.
S-till another class of non-ionic products are the oxyalky- ¦
lated higher aliphatic alcohols. The fatty alcohols should contain at least 6 carbon atoms, and preferably at least about l8 carbon atoms- The most preferred alcohols are lauryl, myri-styl, cetyl, stearyl and oleyl alcohols and the acid alcohols should be condensed with at least about 6 moles of ethylene oxide, and preferably about lO to 30 moles of ethylene oxide..
,A typical non-ionic product is oleyl alcohol condensed with 15 moles of ethylene oxide.
,' i The amount of non-ionic may generally be varied.from about 0 2-3 0~o by weight of the total formulation, depending 'lon the specific nature of the non-ionic utilized, as well as lon the amounts and nature of the oth~ringredients in the oral ¦ .-iformulation.
Although this invention has been described with referenceto specific examples, it will be apparent to one skilled in the art that various modifications may be made thereto which fall within its scope.
; _ _ ._ . , , ,.. ,, . . ... _ , . .. . _~,,
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A non-astringent tasting oral composition to control mouth odor con-taining as the essential agent, a zinc-polymer complex having a pH of about 4.5 to 6 and comprising about 0.01 to 5% by weight of the composition of a zinc compound and about 0.1 to 10% by weight of the composition of an anionic poly-mer wherein said polymer is anionic, linear and contains ionizable carboxyl, sulfonic or phosphonic groups selected from the group consisting of
1. a copolymer of maleic anhydride with ethylene, or styrene, or isobutylene, or polymethyl vinyl ether, or polyethylvinyl ether, having recurring groups:
wherein M and M1 are individually hydrogen, sodium, potassium or ammonium and may be the same or different, and X is ethylene, styrene, isobutylene, methyl-vinyl ether, and ethylvinyl ether, 2. a polyacrylic acid and polyacrylates thereof having recurring groups:
wherein M and M1 have the same meaning as above, 3. a polyitaconic acid and polyitaconates thereof having recurring groups:
wherein M and M1 have the same meaning as above, 4. a polyolefin sulfonate having recurring groups:
wherein M has the same meaning as above, 5. a polyvinyl phosphonate having recurring groups:
wherein M and M1 have the same meaning as above, 6. and a polyvinyl phosphate having recurring groups:
wherein M and M1 have the same meaning as above, and is ionically bound to a physiologically acceptable zinc salt selected from the group consisting of zinc alpha-glucoheptonate zinc stearate zinc gluconate zinc sulfanilate zinc glycerophosphate zinc tartrate zinc hydroxide zinc tellurate zinc 8-hydroxyquinoline zinc tungstate zinc 12-hydroxystearate zinc valerate zinc iodide zinc vanadate zinc acrylate zinc tribromosalicylanilide zinc oxide zinc ricinoleate zinc propionate, the ratio of zinc salt to anionic polymer being within the range of about 2:1 to 1:4.
wherein M and M1 are individually hydrogen, sodium, potassium or ammonium and may be the same or different, and X is ethylene, styrene, isobutylene, methyl-vinyl ether, and ethylvinyl ether, 2. a polyacrylic acid and polyacrylates thereof having recurring groups:
wherein M and M1 have the same meaning as above, 3. a polyitaconic acid and polyitaconates thereof having recurring groups:
wherein M and M1 have the same meaning as above, 4. a polyolefin sulfonate having recurring groups:
wherein M has the same meaning as above, 5. a polyvinyl phosphonate having recurring groups:
wherein M and M1 have the same meaning as above, 6. and a polyvinyl phosphate having recurring groups:
wherein M and M1 have the same meaning as above, and is ionically bound to a physiologically acceptable zinc salt selected from the group consisting of zinc alpha-glucoheptonate zinc stearate zinc gluconate zinc sulfanilate zinc glycerophosphate zinc tartrate zinc hydroxide zinc tellurate zinc 8-hydroxyquinoline zinc tungstate zinc 12-hydroxystearate zinc valerate zinc iodide zinc vanadate zinc acrylate zinc tribromosalicylanilide zinc oxide zinc ricinoleate zinc propionate, the ratio of zinc salt to anionic polymer being within the range of about 2:1 to 1:4.
2. A composition in accordance with claim 1, wherein said anionic poly-mer is a copolymer of maleic anhydride and methylvinyl ether.
3. A composition in accordance with claim 1, wherein said zinc compound is zinc oxide.
4. A composition in accordance with claim 1, wherein said zinc compound is zinc chloride.
5. A composition in accordance with claim 1, wherein said zinc compound is zinc propionate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/691,262 US4138477A (en) | 1976-05-28 | 1976-05-28 | Composition to control mouth odor |
| US691,262 | 1976-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084846A true CA1084846A (en) | 1980-09-02 |
Family
ID=24775812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,803A Expired CA1084846A (en) | 1976-05-28 | 1977-05-05 | Zinc salt and anionic polymer to control mouth odor |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4138477A (en) |
| CA (1) | CA1084846A (en) |
Families Citing this family (198)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4183914A (en) * | 1977-12-19 | 1980-01-15 | Abdul Gaffar | Magnesium polycarboxylate complexes and anticalculus agents |
| US4144323A (en) * | 1978-06-15 | 1979-03-13 | Lever Brothers Company | Novel anticalculus compositions |
| US4339432A (en) * | 1979-06-20 | 1982-07-13 | Lever Brothers Company | Oral mouthwash containing zinc and glycine |
| US4425325A (en) | 1979-06-20 | 1984-01-10 | Lever Brothers Company | Oral compositions |
| US4416867A (en) * | 1979-06-20 | 1983-11-22 | Lever Brothers Company | Oral compositions |
| US4296096A (en) * | 1979-07-05 | 1981-10-20 | Colgate-Palmolive Company | High viscosity dentifrice |
| EP0026252A1 (en) * | 1979-09-27 | 1981-04-08 | Blendax-Werke R. Schneider GmbH & Co. | Oral hygiene composition |
| US4362713A (en) * | 1980-07-25 | 1982-12-07 | Johnson & Johnson Products Inc. | Salts of maleic acid copolymers as dental plaque barrier agents |
| US4362712A (en) * | 1980-07-25 | 1982-12-07 | Johnson & Johnson Products, Inc. | Carboxylated naphthalene formaldehyde condensation polymers as dental plaque barriers |
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| WO2017193284A1 (en) * | 2016-05-10 | 2017-11-16 | Colgate-Palmolive Company | Alginate dentifrice compositions and methods of making thereof |
| WO2019032811A1 (en) | 2017-08-09 | 2019-02-14 | The Procter & Gamble Company | Aptamers for consumer product compositions |
| JP2021500014A (en) | 2017-10-19 | 2021-01-07 | フィリップ・モーリス・プロダクツ・ソシエテ・アノニム | Aerosol generating article with removable freshener segment |
| US20190175486A1 (en) | 2017-12-07 | 2019-06-13 | Johnson & Johnson Consumer Inc. | Oral Care Compositions |
| US20190175487A1 (en) | 2017-12-07 | 2019-06-13 | Johnson & Johnson Consumer Inc. | Oral Care Compositions |
| MX2020006254A (en) | 2017-12-18 | 2020-09-07 | Gaba Int Holding Gmbh | Oral care compositions. |
| US11172873B2 (en) | 2018-05-17 | 2021-11-16 | The Procter & Gamble Company | Systems and methods for hair analysis |
| WO2019222340A1 (en) | 2018-05-17 | 2019-11-21 | The Procter & Gamble Company | Systems and methods for hair coverage analysis |
| US11384357B2 (en) | 2018-06-29 | 2022-07-12 | The Procter And Gamble Company | Aptamers for personal care applications |
| EP3956451A1 (en) | 2019-04-16 | 2022-02-23 | The Procter & Gamble Company | Aptamers for odor control applications |
| WO2020219323A1 (en) | 2019-04-26 | 2020-10-29 | The Procter & Gamble Company | Reduction of tooth staining derived from cationic antimicrobials |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1593485A (en) * | 1925-06-29 | 1926-07-20 | Crosnier Georges Eugene Edme | Antiseptic product |
| US3070510A (en) * | 1959-11-03 | 1962-12-25 | Procter & Gamble | Dentifrice containing resinous cleaning agents |
| US3429963A (en) * | 1964-06-09 | 1969-02-25 | Colgate Palmolive Co | Dental preparation containing polymeric polyelectrolyte |
| US4022880A (en) * | 1973-09-26 | 1977-05-10 | Lever Brothers Company | Anticalculus composition |
| US3943267A (en) * | 1974-05-17 | 1976-03-09 | Neil J. Randol | Method of remineralizing and immunizing tooth enamel for the prevention and control of tooth decay and dental caries |
| US3956480A (en) * | 1974-07-01 | 1976-05-11 | Colgate-Palmolive Company | Treatment of teeth |
-
1976
- 1976-05-28 US US05/691,262 patent/US4138477A/en not_active Expired - Lifetime
-
1977
- 1977-05-05 CA CA277,803A patent/CA1084846A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4138477A (en) | 1979-02-06 |
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