CA1148088A - Dental cream compositions containing a binary fluorine-providing system and dicalcium phosphate - Google Patents
Dental cream compositions containing a binary fluorine-providing system and dicalcium phosphateInfo
- Publication number
- CA1148088A CA1148088A CA000367051A CA367051A CA1148088A CA 1148088 A CA1148088 A CA 1148088A CA 000367051 A CA000367051 A CA 000367051A CA 367051 A CA367051 A CA 367051A CA 1148088 A CA1148088 A CA 1148088A
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- CA
- Canada
- Prior art keywords
- dental
- sodium
- fluorine
- fluoride
- ppm
- 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.)
- Expired
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Classifications
-
- 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
- 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
- A61K8/20—Halogens; Compounds thereof
- A61K8/21—Fluorides; Derivatives 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
Abstract
ABSTRACT
There is disclosed a dental cream composition comprising a dental vehicle, a binary fluorine-providing system which provides about 1000-1670 ppm fluorine from sodium monofluorophosphate and sodium fluoride wherein said sodium fluoride provides about 30-35% by weight of the fluorine in amount of about 300-580 ppm and intimately dispersed in said vehicle and in direct contact with said binary fluorine-providing system components about 20-75%
by weight of a dentally acceptable water-insoluble polishing material consisting essentially of dicalcium phosphate.
There is disclosed a dental cream composition comprising a dental vehicle, a binary fluorine-providing system which provides about 1000-1670 ppm fluorine from sodium monofluorophosphate and sodium fluoride wherein said sodium fluoride provides about 30-35% by weight of the fluorine in amount of about 300-580 ppm and intimately dispersed in said vehicle and in direct contact with said binary fluorine-providing system components about 20-75%
by weight of a dentally acceptable water-insoluble polishing material consisting essentially of dicalcium phosphate.
Description
1148~88 1.
This invention relates to a dental cream composition for promotion of oral hygiene, for example for reducing caries formation and enamel solubility and for promotion of remineralisation of dental enamel 5. which has been demineralised.
Dental cream containing sodium monofluorophosphate and dicalcium phosphate is effective in reducing formation of dental caries. It is also desirable that a dental cream promotes remineralisation of dental 10. enamel. To this end, in accordance with the present invention, the dental cream containing sodium mono-fluorophosphate is modified to incorporate therein a single additional fluorine-containing component, i.e.
sodium fluoride, in amo~ t and ratio with regard to 15. sodium monofluorophcsphate indicated below. It is quite unexpected that such a dental cream would provide improvements in promotion of oral hygiene since sodium fluoride is incompatible with dicalcium phosphate, (dihydrate, anhydrous or mixtures thereof), However, it 20. does indeed reduce caries formation by effecting a high level of fluoride "uptake" into dental enamel, reducing enamel solubility and promoting remineralisation.
Furthermore, prior art relative to dental creams containing a mixture of sodium monofluorophosphate and 25. sodium fluoride does not lead one skilled in the art to the present invention.
British Patent No. 1,514,942 to Foward et al (Beecham Group) describes an oral hygiene composition containing an ammonium salt in which a mixture of 1~48~88
This invention relates to a dental cream composition for promotion of oral hygiene, for example for reducing caries formation and enamel solubility and for promotion of remineralisation of dental enamel 5. which has been demineralised.
Dental cream containing sodium monofluorophosphate and dicalcium phosphate is effective in reducing formation of dental caries. It is also desirable that a dental cream promotes remineralisation of dental 10. enamel. To this end, in accordance with the present invention, the dental cream containing sodium mono-fluorophosphate is modified to incorporate therein a single additional fluorine-containing component, i.e.
sodium fluoride, in amo~ t and ratio with regard to 15. sodium monofluorophcsphate indicated below. It is quite unexpected that such a dental cream would provide improvements in promotion of oral hygiene since sodium fluoride is incompatible with dicalcium phosphate, (dihydrate, anhydrous or mixtures thereof), However, it 20. does indeed reduce caries formation by effecting a high level of fluoride "uptake" into dental enamel, reducing enamel solubility and promoting remineralisation.
Furthermore, prior art relative to dental creams containing a mixture of sodium monofluorophosphate and 25. sodium fluoride does not lead one skilled in the art to the present invention.
British Patent No. 1,514,942 to Foward et al (Beecham Group) describes an oral hygiene composition containing an ammonium salt in which a mixture of 1~48~88
2.
sodium monofluorophosphate and sodium fluoride mzy be present and in which the polishing agent could be hydrated or anhydrous dicalcium phosphate. British Patent No. 1~435,624 to Foward (Beecham ~roup) describes an oral hygiene composition in which a mixture of sodium monofluorophosphate and sodium fluoride is also present and in which the dental abra~ive (polishing agent) is calcium carbonate alone or in admixture with a further dental abrasive, such as hydrated or anhydrous dicalcium 10. phosphate.
In each of the two patents discussed above the mixture of fluorine-containing materials is present in amount such that ~ 80% by weight of the fluoride content is provided by the sodium fluoride. Indeed, in British 15. Patent No, 1,435,624 it is indicated that low amounts of sodium fluoride should be avoided since inactivation by calcium carbonate would occur up to a threshold level.
On the contrary, in the present invention, sodium ~luoride is present as a separate ingredient from 20. sodium monofluorophosphate in amount corresponding to only about 30-35~ by weight of the fluorine content of the toothpaste.
U.S. Patent No. ~,098,878 to Baines et al (Colgate-Palmolive) teaches in Examples 6 and 7 thereof 25. dentifrices containing sodium monofluorophosphate and sodium fluoride and dicalcium phosphate dihydrate abrasive encapsulated in stearic acid. In the present invention it has been found that dicalcium phosphate can provide improved dental hygiene even when it is 30. intimately mixed in the dental cream vehicle with the 1~48088 two fluorine-containing compounds, and this in spite of the incompatibility of sodium ~luoride and dicalcium phosphate.
British Patent No. 1,544,537 toBaines et al~Colgate-5. Palmolive) discloses dentifrices containing sodiummonofluorophosphate and sodium fluoride with alumina trihydrate polishing material which has had its surface modified . One of the modifying agents may be dicalcium phosphate. However, as a surface-modifying agent it can 10. only comprise a small amount of the dentifrice of this patent and not the amount of 20-75% by weight which characterises the present invention.
U.S.Patent No. 4,152,419 to Pensak (Colgate-Palmolive) discloses a dentifrice composition containing a 15. mixture of sodium monofluorophosphate and sodium fluoride and an insoluble sodium monophosphate polishing agent.
A minor amount of dicaicium phosphate (up to about 12%
by weight of the total polishing material 3 may also be present. The fluoride retention results set forth in 20. this patent are synergistic, beyond what would be expected from dicalcium phosphate being compatible with each of sodium monofluorophosphate and sodium fluoride separately. This is quite different from the present invention since an improvement in oral hygiene would 25. not be expected with sodium fluoride, as the only fluoride compound present, owing to the incompatibility with dicalcium phosphate.
U.S. Patent No. ~,95~ ~08 to Agricola et al (Procter & Gamble) discloses compositions containing 30. various phosphorus-containing anticalculus agents and sodium ~onofluorophosphate which are compatible with -`-" 1148~88 4.
cosmetic silicate fillings, such as may be used on front teeth. ~icalcium phosphate is one of many possible abrasives mentioned. It is set for~h that an additional material which provides fluoride ions in water, such as 5. sodiwm fluoride may be present. However, fluoride from sodium fluoride is said to be present in an amount less than about 300 ppm of free fluoride ions in order to avoid damage to silicate fillings by the composition comprising the phosphorus-containing anticalculus agent.
10. In the present invention, the amount of f~uoride provided by sodium fluoride is about 300-580 ppm.
Swedish Patent No. 376,169 (Astra Chemical Products) describes a dentifrice containing calcium monfluoro-phosphate and dicalcium phosphate. There may be 0.1%
15. fluorine from calcium monofluorophosphate (1000 ppm) or up to half of the fluorine (500 ppm) may be replaced by sodium fluoride andtor sodium monofluorophosphate.
Thus, the total system with three fluorine-containing compounds does not provide more than 500 ppm fluorine 20. from sodium fluoride and sodium monofluorophosphate.
This is quite different from the dental cream of the present invention in which a binary fluorine-containing system of sodium monofluorophosphate and sodium fluoride provides about 100~-1670 ppm of fluorine.
25. Further disclosures in the prior art of oral compositions containing sodium monofluorophosphate and sodium fluoride but which differ substantially from the present invention occur in Journal of the Society of Cosmetic Chemistry, Volume 25, pages 3 - 11 (1974), 30. "The Stability of the Monofluorophosphate and Fluoride `` 11~8~88 5.
Ions in Dentifrice Containing Calcium Carbo~ate" by Norén et al (dicalcium phosphate is not disclosed); Extrait de L'~nformation Dentaire, No. 25 (June 18th, 1970);
"Contribution A L'Etude de L'Eficacité de Dentifrices 5. ~luores" by Held et al (calcium carbonate and silica polishing agents); New Zealand Dental Journal, Volume 70, pages 95-108 (April, 1974); "A Laboratory Evaluation of New Zealand Fluoride Toothpastes" by Pearce (ionised fluoride content inherent in sodium monofluorophosphate 10. toothpastes, no separately added fluoride,; and U.S.
Patent No. 3,927,202 to Harvey et al (Colgate-Palmolive), German U.S. 19 65 046 to Rau (Blendax-Werke) and French Patent 2,135,257 (Blendax-Werke), each with incidental disclosures of mixed fluorine-containing compounds with 15. no disclosures of dicalcium phosphate.
In accordance with certain of its aspects the invention relates to a dental cream composition comprising a dental vehicle, a binary fluorine-providing system which provides about 1000 - 1670 ppm fluorine 20. from sodium monofluorophosphate and sodium fluoride wherein said sodium fluoride provides about 30-35% by weight of the fluorine in amount of about 300-580 ppm and intimately dispersed in said vehicle and in direct contact with said binary fluorine-providing system 25. components about 20-75% by weight of a dentally acceptable water-insoluble polishing material consisting essentially of dicalcium phosphate.
It is an advantage of this invention that a dental cream which is effective in reducing caries formation 30. and the solubility of dental enamel in acid is provided.
~48~)~38 6.
It is a further advantage that remineralisation of dental enamel is promoted and a high degree of fluoride "uptake" into dental enamel is provided. Other advantages of this invention will be apparent from consideration of 5. the disclosure.
Sodium monofluorophosphate is used in amount to provide about 700-1090 ppm fluorine to the dental cream in which the total amount of fluorine is about 1000-1670, with about 30-35% by weight to the total fluorine being 10. provided by sodium fluoride (about 300-5&0 ppm). This corresponds to about 0 5-1.2% by weight of sodium monofluorophosphate and about Q.06-0.11% by weight of sodium fluoride. Preferably, the dental cream contains about 1000-1500 ppm, most preferably, about 950-1000 ppm 15. fluorine provided by sodium monofluorophosphate and about 450-500 ppm provided by sodium fluoride.
Sodium monofluorophosphate, Na2P03F, which, as commercially available, may vary considerably in purity.
It may be used in any suitable purity provided that any 20. impurities do not substantially adversely affect the desired properties. In general, the purity is desirably at least 80%. For best results, it should be at least 85%, and preferably at least 90% by weight of sodium monofluorophosphate with the balance being primarily 25. impurities or by-products of manufacture such as sodium fluoride and water-soluble sodium phosphate salt.
Expressed in another way, the sodium monofluorophosphate employed should have a total fluoride content of above 12~, preferably above 12.7%, a content of not more than 30. 1.5~, preferably not more than 1.2% of free sodium 8~88 7.
fluoride; and a sodium monofluorophosphate content of at least 12%, preferably at least 12.1% all calculated as fluorine.
As indicated above, sodium fluoride is present as 5. a separate fluorine-containing component from sodium monofluorophosphate. About ~0~-580 ppm of fluorine is provided to the dental cream by sodium fluoride.
The dental cream contains about 20-75% by weight, preferably about 40-55% of a dentally acceptable water-10. insolub;e polishing material which consists essentiallyof dicalcium phosphate. Dicalcium phosphate may be employed in its dihydrated or anyhydrous forms or as mixtures thereof in any desired ratio. It is preferably the sole polishing agent, but if desired minor amounts 15. (e.g. up to about 5% by weight of the dental cream and up to about 12% by weight of the total polishing material) of other dentally acceptable water-insoluble polishing agents which do not substantially interfere with the ability of the composition of the invention to 20. promote oral hygiene may be present. Typical polishing agents are alumina, silica, sodium aluminosilicate etc. A minor amount of hydrated alumina (e.g. about 1%) also inhibits or even eliminates the tendency of some dental creams to separate or "bleed" in their tubes.
25. The binary fluoride system (sodium mor.ofluoro-phosphate and sodium fluoride) and polishing material are intimately dispersed in the dental vehicle and in direct contact with each other therein.
In the dental cream formulation the liquids and 30. solids should be proportioned to form an extrudable ~.
creamy mass of desirable consistency. In general, liquids in the dental cream will comprise chiefly water, glycerine, sorbitol, propylene glycol, or the like, including suitable mixtures thereof. It is advantageous 5. usually to use a mixture of both water and a humectant or binder such as glycerine or sorbitol. It is preferred to use glycerine. The total liquid content will generally be about 20-75~ by weight of the formulation. It is preferred to use also a gelling agent in dental creams 1O. such as the natural and synthetic gum and gum-like material, e.g., Irish moss, gum tragacanth, sodium carboxymethylcellulose, polyvinylpyrrolidone and starch. ~urther gelling agents include water soluble, hydrophilic colloidal carboxyvinyl polymers, such as 15. those sold under the trademar~ Carbopol 934 and 940 and synthetic inorganic silicated clays such as those sold under the trademark Laponite. The gelling agent content is ~enerally up to about 10~ and preferably about 0.5 -5% by weight of the dental cream.
20. Any suitable surface active or detersive material may be included in the dentifrice compositions. Such compatible materials are desirable to provide additional detersive, foaming and antibacterial properties depen-ding upon the specific type of surface active material 25. and are selected similarly. These detergents are water-soluble compounds usually, and may be anionic, nonionic or cationic in structure. It is usually preferred to use the water-soluble non-soap or synthetic organic detergents. Suitable detersive materials are ~0. known and include, for example, the water-soluble salts 8~88 9.
of higher fatty acid monoglyceride monosulphate detergent (e.g., sodium coconut fatty acid monoglyceride mono-sulphate), higher alkyl sulphate (e.g., sodium lauryl sulphate), alkyl aryl sulphonate (e.g., sodium dodecyl 5. benzene sulphonate, higher fatty acid esters of 1,2-dihydroxy propane sulphonate) and the like.
Further surface active agents include the substan-tially saturated higher aliphatic acyl amides of lower aliphatic amino carboxyIic acid compounds, such as 10. those having 12 to 16 carbons in the acyl~radical. The amino acid portion is derived generally from the lower aliphatic saturated monoaminocarboxylic acids having about 2 to 6 carbons, usually the monocarboxylic acid compounds. Suitable compounds are the fatty acid 15. amides of glycine, sarcosine, alanine, 3-aminopropanoic acid and valine having about 12 to 16 carbons in the acyl group. It is preferred to use the N-lauroyl, myristoyl and palmitoyl sarcoside compounds, however, for optimum effects.
20. The amide compounds may be employed in the form of the free acid or preferably as the water-soluble salts thereof, such as the alkali metal, ammonium, amine and alkylolamine salts. Specific examples thereof are sodium and potassium N-lauroyl, myristoyl and palmitoyl 25. sarcosides, ammonium and ethanolamine N-lauroyl sarco-side, N-lauroyl sarcosine, and sodium N-lauroyl glycide and alanine. For convenience herein, reference to "amino carboxylic acid compound," "sarcoside," and the like refers to such compounds having a free carboxylic 30. group or the water-soluble carboxylate salts.
1148~88 10.
Such materials are utilized in pure or substantially pure form. They should be as free as practicable from soap or similar higher fatty acid material which tends to reduce the activity of these compounds. In usual 5. practice, the amount of such higher fatty acid material is less than 15% by weight of the amide and insufficient to substantially adversely affect it, and preferably less than a~out 10% of said amide material.
Various other materials may be incorporated in the 10. dental creams of this invention. Examples thereof are colouring or whitening agents, preservatives, silicones, chlorophyll compounds and ammoniated materials such as urea, diammonium phosphate and mixtures thereof. These adjuvants are incorporated in the instant composition 15. in amounts which do not substantially adversely affect the properties and characteristics suitably selected and used in proper amount depending upon the particular type of preparation involved.
For some purposes it may be desirable to include 20. antibacterial agents in the compositions of the present invention. Typical antibacterial ager.ts which may be used in amounts of about 0.01% to about 5%, preferably about 0.05% to about 1.0%, by weight of the dentifrice composition include:
25. N1-4 (chlorobenzyl) - N5 - (2,4-dichlorobenzyl) biguanide;
11~8~88 1 1 .
p-chlorophenyl biguanide;
4-chlorobenzyhydryl biguanide;
4-chlorobenzhydrylguanylurea;
N~3-lauroxypropyl-N -p-chlorobenzylbiguanide;
5. 1,6-di-p-chlorophenylbiguanidehexane;
1-(lauryldimethylammonium)-8-(p-chlorobenzyl-dimethylammonium) octane dichloride;
5,6-dichloro-2-guanidinobenzimidazole;
N1-p-chlorophenyl-N5-laurylbiguanide;
1O. 5-amino-1,3-bis (2-ethylhexyl)-5-methylhexahy-dropyrimidine;
and their non-toxic acid addition salts.
Any suitable flavouring or sweetening materials may be employed in formulating a flavour for the compo-15. sitions of the present invention Examples of suitable flavouring constituents include the flavouring oils, e.g., oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, as well as methylsalicylate. Suitable 20. sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, sodium saccharine dipeptides of U.S. Patent No. 3,9~9,261 and oxathiazin salts of U.S. Patent No. 3,932,606. Suitably, flavour and sweetening agent may together comprise from about 0.01 5. to 5% or more of the instant invention.
The dental creams should have a pH practicable for use. A pH range of 5 to 9 is particularly desirable.
The reference to the pH is meant to be the pH determina-tion directly on the toothpaste. If desired, materials ~0. such as benzoic acid or citric acid may be added to ~8088 12.
adjust the pH to say 5.5 to 6.5.
The dental cream is typically packaged in an extrudible tube, such as unlined aluminium or lead, or in a pressurised container.
5. The following specific example further illu-strative of the nature of the present invention, but it is to be understood that the invention is not limited thereto. The compositions are prepared in the usual manner and all amountsof the various ingredients are by 0. weight unless otherwise specified.
Example The following dental creams are prepared by conventional dental cream formulation technique and evaluated with regard to effects in promoting dental 15. hygiene: A(%) B(~) C(%) D(%) E(%) Glycerol 22.00 22.00 22.00 22.00 22.00 Sodium ~g~eethyl 1.10 0~90 1.10 1.10'0.90 Sodium Saccharin 0.20 0.20 0.200.20 0.20 20. Tetrasodium 0 50 0 50 pyrophosphate Benzoic acid 0.20 - 0.30 0.20 Water 22.20 25.24 21.24 21.3825.28 fluorophosphate ~ 0.76 0.76 0.820.82 25. Sodium fluoride - 0.10 0.10 D calcium phos- 48.00 - _48.00 (ydrate*d3a3l3U)mina52.00 ~ 52.0052.00 30. sulphate 1.50 1.50 1.50 1.501.50 Flavour 0.80 0.80 0.80 0.800.80 *Trademark 11~8~88 1 3 .
. All parts percentage by weight.
Dental creams A (non-fluoride placebo with hydrated alumina); B (binary fluorine pro~iding system with dicalcium phosphate in accordance with the present 5. invention); C (binary fluorine providing system with hydrated alumina); and D (sodium monofluorophosphate with hydrated alumina) are evaluated for retention of soluble fluorine and soluble fluoride ion at room temperature with the following results:
10. Table I
Soluble fluorine in ppm Dental I t- l 1 3 6 1 2 cream nl la-- month months months year years 15. B1130 990 870 710 640 420 C1210 1110 1040 g60 900 800 D 890 820 740 650 6~o 450 Soluble fluoride ion in ppm 25. Dental creams B, C, D and E (sodium monofluoro-phosphate and dicalcium phosphate) are subjected to an enamel solubility reduction to determine solubility of enamelCntacted with a buffered acid and each dental cream with the following results:
~481~88 4 .
.
TABL~ II
Dental CreamsPercent of enamel solubilitv reduction ., B 12.7 C 23.4 D 3.7 E 1.4 Dental creams B, C and D are compared with a control of distilled water to determine in vitro remineralisat~n of dental enamel with the following results:
T~BLE III
CompositionMean Percent Remineralisation Distilled Water _3.3 , Dental Cream ....
B +12.7 C -16.4 D -23.7 i : The uptake of fluoride ion by dental enamel with dental creams A, B, C and D is determined with the . following results on 10 thin enamel layers of bovine incisors (the depth of each layer in millimicrons is indicated in parenthesis pelow the fluoride uptake . figures):
.
~ 1~8088 u~ _~ ~ ~ 15.
_ ~~ N ~ 1~ 0 _ ~ ~ ~
01 ~ . J N O
,~_ ~ ~
J ~ J O
~ ~ 0 ~ ~ .
h _ N O
~ __ +, ~ 0u~ ~ c~ ~ ~ 0 ~1 ~ ,~ N C~i _ N O N ~
~ -- _ _ ~ J¦ ~ . 0 N~ J
1:4 ~ O~J U~
------ ~
ot~ oJ~;~ ~
~ _ _ ~`J¦ NO t' O O
_ ~¦ ~D N 11~ J J 0 ~
D U~ J-~O ~C)U) ~ ~ ~ m ~) ~
~ C~
8~88 16.
It is ncted that fluoride uptake found with placebo dental cream A would be due to fluoride independently present in the dental enamel enamel.
Soluble fluorine and soluble ~luoride ion levels 5. (Table I) are determined by routine laboratory techniques.
Enamel solubility evaluations (Table II) are determined on enamel powdered from extracted human teeth with enamel separated from dentine. Dental cream solutions are contacted with the powdered enamel and then 10. a ~er drying the enamel is etched with a~buffered acid solution. The percent of reduction in enamel solubility is determined by comparison of the amount enamel contacted with test dental creams in comparison to a control which is dissolved.
15. Remineralisation evaluations (Table III) are determined with human intact premolars which are first demineralised on a portion of the teeth with a buffered acid gel. To determine the amount of mineral removed from a sample tooth ~ a portion of the demineralised 20. surface of the remaining teeth are then treated with a control solution or slurries of the test dental creams.
Fluoride uptake evaluations (Table IV) are determined on blocks of cleaned bovine incisors which are immersed in an acid buffered solution containing 25. hydroxyapatite and stirred for one hour at 37C with slurries of the test dental creams. The dental creams are then removed from demineralised white spot blocks and placed in a metastable solution of simulated saliva to eliminate unreacted fluoride. Ten thin enamel layers 30. are re=oved iFom the blocks oi bovine ensmel snd the - , -` ~148~88 17.
.
depths of each level and fluoride content o~ each level determined.
The results set forth in Tables I-IV show that while dental creams B, C and D effectively retain 5. desirable levels of soluble fluorine and soluble fluoride ion upon aging (Table I) only dental creams B and C reduce solubility of dental enamel in comparison I with dental creams D and E (Table II) and only dental ; cream B promotes remineralisation in comparison with 10. dental creams C and D (Table III) and den'tal cream B
is generally more effective in promoting fluoride uptake of dental enamel than dental creams C and D, particu-larly in l:be deeper (~-10) layers (Ta le IV).
;
sodium monofluorophosphate and sodium fluoride mzy be present and in which the polishing agent could be hydrated or anhydrous dicalcium phosphate. British Patent No. 1~435,624 to Foward (Beecham ~roup) describes an oral hygiene composition in which a mixture of sodium monofluorophosphate and sodium fluoride is also present and in which the dental abra~ive (polishing agent) is calcium carbonate alone or in admixture with a further dental abrasive, such as hydrated or anhydrous dicalcium 10. phosphate.
In each of the two patents discussed above the mixture of fluorine-containing materials is present in amount such that ~ 80% by weight of the fluoride content is provided by the sodium fluoride. Indeed, in British 15. Patent No, 1,435,624 it is indicated that low amounts of sodium fluoride should be avoided since inactivation by calcium carbonate would occur up to a threshold level.
On the contrary, in the present invention, sodium ~luoride is present as a separate ingredient from 20. sodium monofluorophosphate in amount corresponding to only about 30-35~ by weight of the fluorine content of the toothpaste.
U.S. Patent No. ~,098,878 to Baines et al (Colgate-Palmolive) teaches in Examples 6 and 7 thereof 25. dentifrices containing sodium monofluorophosphate and sodium fluoride and dicalcium phosphate dihydrate abrasive encapsulated in stearic acid. In the present invention it has been found that dicalcium phosphate can provide improved dental hygiene even when it is 30. intimately mixed in the dental cream vehicle with the 1~48088 two fluorine-containing compounds, and this in spite of the incompatibility of sodium ~luoride and dicalcium phosphate.
British Patent No. 1,544,537 toBaines et al~Colgate-5. Palmolive) discloses dentifrices containing sodiummonofluorophosphate and sodium fluoride with alumina trihydrate polishing material which has had its surface modified . One of the modifying agents may be dicalcium phosphate. However, as a surface-modifying agent it can 10. only comprise a small amount of the dentifrice of this patent and not the amount of 20-75% by weight which characterises the present invention.
U.S.Patent No. 4,152,419 to Pensak (Colgate-Palmolive) discloses a dentifrice composition containing a 15. mixture of sodium monofluorophosphate and sodium fluoride and an insoluble sodium monophosphate polishing agent.
A minor amount of dicaicium phosphate (up to about 12%
by weight of the total polishing material 3 may also be present. The fluoride retention results set forth in 20. this patent are synergistic, beyond what would be expected from dicalcium phosphate being compatible with each of sodium monofluorophosphate and sodium fluoride separately. This is quite different from the present invention since an improvement in oral hygiene would 25. not be expected with sodium fluoride, as the only fluoride compound present, owing to the incompatibility with dicalcium phosphate.
U.S. Patent No. ~,95~ ~08 to Agricola et al (Procter & Gamble) discloses compositions containing 30. various phosphorus-containing anticalculus agents and sodium ~onofluorophosphate which are compatible with -`-" 1148~88 4.
cosmetic silicate fillings, such as may be used on front teeth. ~icalcium phosphate is one of many possible abrasives mentioned. It is set for~h that an additional material which provides fluoride ions in water, such as 5. sodiwm fluoride may be present. However, fluoride from sodium fluoride is said to be present in an amount less than about 300 ppm of free fluoride ions in order to avoid damage to silicate fillings by the composition comprising the phosphorus-containing anticalculus agent.
10. In the present invention, the amount of f~uoride provided by sodium fluoride is about 300-580 ppm.
Swedish Patent No. 376,169 (Astra Chemical Products) describes a dentifrice containing calcium monfluoro-phosphate and dicalcium phosphate. There may be 0.1%
15. fluorine from calcium monofluorophosphate (1000 ppm) or up to half of the fluorine (500 ppm) may be replaced by sodium fluoride andtor sodium monofluorophosphate.
Thus, the total system with three fluorine-containing compounds does not provide more than 500 ppm fluorine 20. from sodium fluoride and sodium monofluorophosphate.
This is quite different from the dental cream of the present invention in which a binary fluorine-containing system of sodium monofluorophosphate and sodium fluoride provides about 100~-1670 ppm of fluorine.
25. Further disclosures in the prior art of oral compositions containing sodium monofluorophosphate and sodium fluoride but which differ substantially from the present invention occur in Journal of the Society of Cosmetic Chemistry, Volume 25, pages 3 - 11 (1974), 30. "The Stability of the Monofluorophosphate and Fluoride `` 11~8~88 5.
Ions in Dentifrice Containing Calcium Carbo~ate" by Norén et al (dicalcium phosphate is not disclosed); Extrait de L'~nformation Dentaire, No. 25 (June 18th, 1970);
"Contribution A L'Etude de L'Eficacité de Dentifrices 5. ~luores" by Held et al (calcium carbonate and silica polishing agents); New Zealand Dental Journal, Volume 70, pages 95-108 (April, 1974); "A Laboratory Evaluation of New Zealand Fluoride Toothpastes" by Pearce (ionised fluoride content inherent in sodium monofluorophosphate 10. toothpastes, no separately added fluoride,; and U.S.
Patent No. 3,927,202 to Harvey et al (Colgate-Palmolive), German U.S. 19 65 046 to Rau (Blendax-Werke) and French Patent 2,135,257 (Blendax-Werke), each with incidental disclosures of mixed fluorine-containing compounds with 15. no disclosures of dicalcium phosphate.
In accordance with certain of its aspects the invention relates to a dental cream composition comprising a dental vehicle, a binary fluorine-providing system which provides about 1000 - 1670 ppm fluorine 20. from sodium monofluorophosphate and sodium fluoride wherein said sodium fluoride provides about 30-35% by weight of the fluorine in amount of about 300-580 ppm and intimately dispersed in said vehicle and in direct contact with said binary fluorine-providing system 25. components about 20-75% by weight of a dentally acceptable water-insoluble polishing material consisting essentially of dicalcium phosphate.
It is an advantage of this invention that a dental cream which is effective in reducing caries formation 30. and the solubility of dental enamel in acid is provided.
~48~)~38 6.
It is a further advantage that remineralisation of dental enamel is promoted and a high degree of fluoride "uptake" into dental enamel is provided. Other advantages of this invention will be apparent from consideration of 5. the disclosure.
Sodium monofluorophosphate is used in amount to provide about 700-1090 ppm fluorine to the dental cream in which the total amount of fluorine is about 1000-1670, with about 30-35% by weight to the total fluorine being 10. provided by sodium fluoride (about 300-5&0 ppm). This corresponds to about 0 5-1.2% by weight of sodium monofluorophosphate and about Q.06-0.11% by weight of sodium fluoride. Preferably, the dental cream contains about 1000-1500 ppm, most preferably, about 950-1000 ppm 15. fluorine provided by sodium monofluorophosphate and about 450-500 ppm provided by sodium fluoride.
Sodium monofluorophosphate, Na2P03F, which, as commercially available, may vary considerably in purity.
It may be used in any suitable purity provided that any 20. impurities do not substantially adversely affect the desired properties. In general, the purity is desirably at least 80%. For best results, it should be at least 85%, and preferably at least 90% by weight of sodium monofluorophosphate with the balance being primarily 25. impurities or by-products of manufacture such as sodium fluoride and water-soluble sodium phosphate salt.
Expressed in another way, the sodium monofluorophosphate employed should have a total fluoride content of above 12~, preferably above 12.7%, a content of not more than 30. 1.5~, preferably not more than 1.2% of free sodium 8~88 7.
fluoride; and a sodium monofluorophosphate content of at least 12%, preferably at least 12.1% all calculated as fluorine.
As indicated above, sodium fluoride is present as 5. a separate fluorine-containing component from sodium monofluorophosphate. About ~0~-580 ppm of fluorine is provided to the dental cream by sodium fluoride.
The dental cream contains about 20-75% by weight, preferably about 40-55% of a dentally acceptable water-10. insolub;e polishing material which consists essentiallyof dicalcium phosphate. Dicalcium phosphate may be employed in its dihydrated or anyhydrous forms or as mixtures thereof in any desired ratio. It is preferably the sole polishing agent, but if desired minor amounts 15. (e.g. up to about 5% by weight of the dental cream and up to about 12% by weight of the total polishing material) of other dentally acceptable water-insoluble polishing agents which do not substantially interfere with the ability of the composition of the invention to 20. promote oral hygiene may be present. Typical polishing agents are alumina, silica, sodium aluminosilicate etc. A minor amount of hydrated alumina (e.g. about 1%) also inhibits or even eliminates the tendency of some dental creams to separate or "bleed" in their tubes.
25. The binary fluoride system (sodium mor.ofluoro-phosphate and sodium fluoride) and polishing material are intimately dispersed in the dental vehicle and in direct contact with each other therein.
In the dental cream formulation the liquids and 30. solids should be proportioned to form an extrudable ~.
creamy mass of desirable consistency. In general, liquids in the dental cream will comprise chiefly water, glycerine, sorbitol, propylene glycol, or the like, including suitable mixtures thereof. It is advantageous 5. usually to use a mixture of both water and a humectant or binder such as glycerine or sorbitol. It is preferred to use glycerine. The total liquid content will generally be about 20-75~ by weight of the formulation. It is preferred to use also a gelling agent in dental creams 1O. such as the natural and synthetic gum and gum-like material, e.g., Irish moss, gum tragacanth, sodium carboxymethylcellulose, polyvinylpyrrolidone and starch. ~urther gelling agents include water soluble, hydrophilic colloidal carboxyvinyl polymers, such as 15. those sold under the trademar~ Carbopol 934 and 940 and synthetic inorganic silicated clays such as those sold under the trademark Laponite. The gelling agent content is ~enerally up to about 10~ and preferably about 0.5 -5% by weight of the dental cream.
20. Any suitable surface active or detersive material may be included in the dentifrice compositions. Such compatible materials are desirable to provide additional detersive, foaming and antibacterial properties depen-ding upon the specific type of surface active material 25. and are selected similarly. These detergents are water-soluble compounds usually, and may be anionic, nonionic or cationic in structure. It is usually preferred to use the water-soluble non-soap or synthetic organic detergents. Suitable detersive materials are ~0. known and include, for example, the water-soluble salts 8~88 9.
of higher fatty acid monoglyceride monosulphate detergent (e.g., sodium coconut fatty acid monoglyceride mono-sulphate), higher alkyl sulphate (e.g., sodium lauryl sulphate), alkyl aryl sulphonate (e.g., sodium dodecyl 5. benzene sulphonate, higher fatty acid esters of 1,2-dihydroxy propane sulphonate) and the like.
Further surface active agents include the substan-tially saturated higher aliphatic acyl amides of lower aliphatic amino carboxyIic acid compounds, such as 10. those having 12 to 16 carbons in the acyl~radical. The amino acid portion is derived generally from the lower aliphatic saturated monoaminocarboxylic acids having about 2 to 6 carbons, usually the monocarboxylic acid compounds. Suitable compounds are the fatty acid 15. amides of glycine, sarcosine, alanine, 3-aminopropanoic acid and valine having about 12 to 16 carbons in the acyl group. It is preferred to use the N-lauroyl, myristoyl and palmitoyl sarcoside compounds, however, for optimum effects.
20. The amide compounds may be employed in the form of the free acid or preferably as the water-soluble salts thereof, such as the alkali metal, ammonium, amine and alkylolamine salts. Specific examples thereof are sodium and potassium N-lauroyl, myristoyl and palmitoyl 25. sarcosides, ammonium and ethanolamine N-lauroyl sarco-side, N-lauroyl sarcosine, and sodium N-lauroyl glycide and alanine. For convenience herein, reference to "amino carboxylic acid compound," "sarcoside," and the like refers to such compounds having a free carboxylic 30. group or the water-soluble carboxylate salts.
1148~88 10.
Such materials are utilized in pure or substantially pure form. They should be as free as practicable from soap or similar higher fatty acid material which tends to reduce the activity of these compounds. In usual 5. practice, the amount of such higher fatty acid material is less than 15% by weight of the amide and insufficient to substantially adversely affect it, and preferably less than a~out 10% of said amide material.
Various other materials may be incorporated in the 10. dental creams of this invention. Examples thereof are colouring or whitening agents, preservatives, silicones, chlorophyll compounds and ammoniated materials such as urea, diammonium phosphate and mixtures thereof. These adjuvants are incorporated in the instant composition 15. in amounts which do not substantially adversely affect the properties and characteristics suitably selected and used in proper amount depending upon the particular type of preparation involved.
For some purposes it may be desirable to include 20. antibacterial agents in the compositions of the present invention. Typical antibacterial ager.ts which may be used in amounts of about 0.01% to about 5%, preferably about 0.05% to about 1.0%, by weight of the dentifrice composition include:
25. N1-4 (chlorobenzyl) - N5 - (2,4-dichlorobenzyl) biguanide;
11~8~88 1 1 .
p-chlorophenyl biguanide;
4-chlorobenzyhydryl biguanide;
4-chlorobenzhydrylguanylurea;
N~3-lauroxypropyl-N -p-chlorobenzylbiguanide;
5. 1,6-di-p-chlorophenylbiguanidehexane;
1-(lauryldimethylammonium)-8-(p-chlorobenzyl-dimethylammonium) octane dichloride;
5,6-dichloro-2-guanidinobenzimidazole;
N1-p-chlorophenyl-N5-laurylbiguanide;
1O. 5-amino-1,3-bis (2-ethylhexyl)-5-methylhexahy-dropyrimidine;
and their non-toxic acid addition salts.
Any suitable flavouring or sweetening materials may be employed in formulating a flavour for the compo-15. sitions of the present invention Examples of suitable flavouring constituents include the flavouring oils, e.g., oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, as well as methylsalicylate. Suitable 20. sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, sodium saccharine dipeptides of U.S. Patent No. 3,9~9,261 and oxathiazin salts of U.S. Patent No. 3,932,606. Suitably, flavour and sweetening agent may together comprise from about 0.01 5. to 5% or more of the instant invention.
The dental creams should have a pH practicable for use. A pH range of 5 to 9 is particularly desirable.
The reference to the pH is meant to be the pH determina-tion directly on the toothpaste. If desired, materials ~0. such as benzoic acid or citric acid may be added to ~8088 12.
adjust the pH to say 5.5 to 6.5.
The dental cream is typically packaged in an extrudible tube, such as unlined aluminium or lead, or in a pressurised container.
5. The following specific example further illu-strative of the nature of the present invention, but it is to be understood that the invention is not limited thereto. The compositions are prepared in the usual manner and all amountsof the various ingredients are by 0. weight unless otherwise specified.
Example The following dental creams are prepared by conventional dental cream formulation technique and evaluated with regard to effects in promoting dental 15. hygiene: A(%) B(~) C(%) D(%) E(%) Glycerol 22.00 22.00 22.00 22.00 22.00 Sodium ~g~eethyl 1.10 0~90 1.10 1.10'0.90 Sodium Saccharin 0.20 0.20 0.200.20 0.20 20. Tetrasodium 0 50 0 50 pyrophosphate Benzoic acid 0.20 - 0.30 0.20 Water 22.20 25.24 21.24 21.3825.28 fluorophosphate ~ 0.76 0.76 0.820.82 25. Sodium fluoride - 0.10 0.10 D calcium phos- 48.00 - _48.00 (ydrate*d3a3l3U)mina52.00 ~ 52.0052.00 30. sulphate 1.50 1.50 1.50 1.501.50 Flavour 0.80 0.80 0.80 0.800.80 *Trademark 11~8~88 1 3 .
. All parts percentage by weight.
Dental creams A (non-fluoride placebo with hydrated alumina); B (binary fluorine pro~iding system with dicalcium phosphate in accordance with the present 5. invention); C (binary fluorine providing system with hydrated alumina); and D (sodium monofluorophosphate with hydrated alumina) are evaluated for retention of soluble fluorine and soluble fluoride ion at room temperature with the following results:
10. Table I
Soluble fluorine in ppm Dental I t- l 1 3 6 1 2 cream nl la-- month months months year years 15. B1130 990 870 710 640 420 C1210 1110 1040 g60 900 800 D 890 820 740 650 6~o 450 Soluble fluoride ion in ppm 25. Dental creams B, C, D and E (sodium monofluoro-phosphate and dicalcium phosphate) are subjected to an enamel solubility reduction to determine solubility of enamelCntacted with a buffered acid and each dental cream with the following results:
~481~88 4 .
.
TABL~ II
Dental CreamsPercent of enamel solubilitv reduction ., B 12.7 C 23.4 D 3.7 E 1.4 Dental creams B, C and D are compared with a control of distilled water to determine in vitro remineralisat~n of dental enamel with the following results:
T~BLE III
CompositionMean Percent Remineralisation Distilled Water _3.3 , Dental Cream ....
B +12.7 C -16.4 D -23.7 i : The uptake of fluoride ion by dental enamel with dental creams A, B, C and D is determined with the . following results on 10 thin enamel layers of bovine incisors (the depth of each layer in millimicrons is indicated in parenthesis pelow the fluoride uptake . figures):
.
~ 1~8088 u~ _~ ~ ~ 15.
_ ~~ N ~ 1~ 0 _ ~ ~ ~
01 ~ . J N O
,~_ ~ ~
J ~ J O
~ ~ 0 ~ ~ .
h _ N O
~ __ +, ~ 0u~ ~ c~ ~ ~ 0 ~1 ~ ,~ N C~i _ N O N ~
~ -- _ _ ~ J¦ ~ . 0 N~ J
1:4 ~ O~J U~
------ ~
ot~ oJ~;~ ~
~ _ _ ~`J¦ NO t' O O
_ ~¦ ~D N 11~ J J 0 ~
D U~ J-~O ~C)U) ~ ~ ~ m ~) ~
~ C~
8~88 16.
It is ncted that fluoride uptake found with placebo dental cream A would be due to fluoride independently present in the dental enamel enamel.
Soluble fluorine and soluble ~luoride ion levels 5. (Table I) are determined by routine laboratory techniques.
Enamel solubility evaluations (Table II) are determined on enamel powdered from extracted human teeth with enamel separated from dentine. Dental cream solutions are contacted with the powdered enamel and then 10. a ~er drying the enamel is etched with a~buffered acid solution. The percent of reduction in enamel solubility is determined by comparison of the amount enamel contacted with test dental creams in comparison to a control which is dissolved.
15. Remineralisation evaluations (Table III) are determined with human intact premolars which are first demineralised on a portion of the teeth with a buffered acid gel. To determine the amount of mineral removed from a sample tooth ~ a portion of the demineralised 20. surface of the remaining teeth are then treated with a control solution or slurries of the test dental creams.
Fluoride uptake evaluations (Table IV) are determined on blocks of cleaned bovine incisors which are immersed in an acid buffered solution containing 25. hydroxyapatite and stirred for one hour at 37C with slurries of the test dental creams. The dental creams are then removed from demineralised white spot blocks and placed in a metastable solution of simulated saliva to eliminate unreacted fluoride. Ten thin enamel layers 30. are re=oved iFom the blocks oi bovine ensmel snd the - , -` ~148~88 17.
.
depths of each level and fluoride content o~ each level determined.
The results set forth in Tables I-IV show that while dental creams B, C and D effectively retain 5. desirable levels of soluble fluorine and soluble fluoride ion upon aging (Table I) only dental creams B and C reduce solubility of dental enamel in comparison I with dental creams D and E (Table II) and only dental ; cream B promotes remineralisation in comparison with 10. dental creams C and D (Table III) and den'tal cream B
is generally more effective in promoting fluoride uptake of dental enamel than dental creams C and D, particu-larly in l:be deeper (~-10) layers (Ta le IV).
;
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A dental cream composition comprising a dental vehicle, a binary fluorine providing system which provides about 1000-1670 ppm fluorine from sodium monofluorophosphate and sodium fluoride wherein said sodium fluoride provides about 30-35% by weight of the fluorine in amount of about 300-580 ppm and intimately dispersed in said vehicle, and in direct contact with said binary fluorine-providing system components about 20-75% by weight of a dentally acceptable water-insoluble polishing material consisting essen-tially of dicalcium phosphate.
2. The dental cream composition claimed in Claim 1 wherein about 1000-1500 ppm of fluoride is provided to said dental cream from said binary fluorine-providing system.
3. The dental cream composition claimed in Claim 1 or Claim 2 wherein about 900-1000 ppm fluorine are provided by sodium monofluorophos-phate and about 450-500 ppm are provided by sodium fluoride.
4. The dental cream composition claimed in Claim 1 wherein about 40-55% of said polishing material is present.
5. The dental cream composition claimed in claim 1 wherein dical-cium phosphate is the only polishing agent present.
6. The dental cream claimed in claim 1 wherein there is present about 0.76% by weight of sodium monofluorophosphate, about 0.1% by weight of sodium fluoride and about 48% by weight of dicalcium phosphate dihydrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7943642A GB2068727B (en) | 1979-12-19 | 1979-12-19 | Dental cream comprising sodium fluoride sodium monofluorophosphate and dicalcium phosphate |
| GB79/43642 | 1979-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148088A true CA1148088A (en) | 1983-06-14 |
Family
ID=10509929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000367051A Expired CA1148088A (en) | 1979-12-19 | 1980-12-18 | Dental cream compositions containing a binary fluorine-providing system and dicalcium phosphate |
Country Status (27)
| Country | Link |
|---|---|
| US (1) | US4357317A (en) |
| JP (1) | JPS5699408A (en) |
| AR (1) | AR223411A1 (en) |
| AT (1) | AT390731B (en) |
| AU (1) | AU536547B2 (en) |
| BE (1) | BE886710A (en) |
| BR (1) | BR8008183A (en) |
| CA (1) | CA1148088A (en) |
| CH (1) | CH644754A5 (en) |
| DE (1) | DE3044448A1 (en) |
| DK (1) | DK156616C (en) |
| ES (1) | ES8107019A1 (en) |
| FR (1) | FR2471782B1 (en) |
| GB (1) | GB2068727B (en) |
| GR (1) | GR72833B (en) |
| IE (1) | IE51063B1 (en) |
| IN (1) | IN155160B (en) |
| IT (1) | IT1188975B (en) |
| NL (1) | NL8006737A (en) |
| NO (1) | NO158204C (en) |
| NZ (1) | NZ195585A (en) |
| PH (1) | PH20455A (en) |
| PT (1) | PT72217A (en) |
| SE (1) | SE448677B (en) |
| ZA (1) | ZA807530B (en) |
| ZM (1) | ZM11080A1 (en) |
| ZW (1) | ZW28980A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4425324A (en) | 1981-05-11 | 1984-01-10 | Colgate-Palmolive Company | Hazed toothpaste |
| NO158361C (en) * | 1981-07-03 | 1988-08-31 | Intradal Nv | DENTAL CARE WITH ANTICARIES EFFECT. |
| US4545979A (en) * | 1982-02-22 | 1985-10-08 | Warner-Lambert Company | Dental hygiene compositions |
| EP0092929B2 (en) * | 1982-04-20 | 1991-05-02 | Beecham Group Plc | Oral hygiene compositions |
| US4885155A (en) * | 1982-06-22 | 1989-12-05 | The Procter & Gamble Company | Anticalculus compositions using pyrophosphate salt |
| US4999184A (en) * | 1982-06-22 | 1991-03-12 | The Procter & Gamble Company | Oral compositions |
| US4515772A (en) * | 1982-06-22 | 1985-05-07 | The Procter & Gamble Company | Oral compositions |
| US4806339A (en) * | 1982-06-22 | 1989-02-21 | The Procter & Gamble Company | Oral compositions |
| US4419346A (en) * | 1982-08-13 | 1983-12-06 | Nabisco Brands, Inc. | Method and composition to inhibit the growth of Streptococcus mutans by the use of saccharin/fluoride combination |
| US4424203A (en) | 1983-03-04 | 1984-01-03 | Pakhomov Gennady N | Gel for dental caries prevention |
| US4415550A (en) * | 1983-03-04 | 1983-11-15 | Pakhomov Gennady N | Treatment-and-prophylactic tooth paste possessing anticarious effect |
| AT388666B (en) * | 1983-03-28 | 1989-08-10 | Colgate Palmolive Co | Dental cream |
| US4550018A (en) * | 1984-02-22 | 1985-10-29 | Warner-Lambert Company | Dental hygiene compositions |
| JPS646213A (en) * | 1987-06-27 | 1989-01-10 | Sangi Kk | Composition for preventing denting caries |
| US5172440A (en) * | 1991-07-09 | 1992-12-22 | Ming Wu L | Quilt bag |
| ES2050079B1 (en) * | 1992-10-07 | 1994-11-16 | Bugallo Juana Diez | TOOTHPASTE. |
| DE4312009C2 (en) * | 1993-04-13 | 1995-06-08 | Henkel Kgaa | Process for the production of sugar surfactants with improved odor quality |
| US6372198B1 (en) | 2000-09-14 | 2002-04-16 | Joseph M. Abbate | Dentifrice for the mineralization and remineralization of teeth |
| WO2017079953A1 (en) | 2015-11-13 | 2017-05-18 | The Procter & Gamble Company | Dentifrice compositions with improved fluoride stability |
| MX2018005915A (en) | 2015-11-13 | 2019-04-04 | Procter & Gamble | Dentifrice compositions with dual fluoride source with improved fluoride uptake. |
| EP3373901B1 (en) | 2015-11-13 | 2019-12-25 | The Procter and Gamble Company | Dentifrice compositions with improved fluoride uptake |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3308029A (en) * | 1963-11-06 | 1967-03-07 | Monsanto Co | Dentifrice compositions comprising dicalcium orthophosphate and sodium monofluorophosphate |
| US3634585A (en) * | 1966-08-11 | 1972-01-11 | Colgate Palmolive Co | Dentifrice preparation |
| DE1965046U (en) | 1967-02-03 | 1967-07-27 | Carl Schmale Fa | CONTROL DEVICE FOR THE AIR SUPPLY TO CHAIN CUTTER DEVICES ON SEWING MACHINES. |
| US3699220A (en) * | 1970-07-10 | 1972-10-17 | Consmetische Fabriek Prondenta | Dentifrice |
| IT987852B (en) | 1971-05-03 | 1975-03-20 | Blendax Werke Schneider Co | DENTRIFICATION PASTA |
| SE376169B (en) | 1972-09-25 | 1975-05-12 | Astra Chem Prod Ab | |
| US3927202A (en) * | 1973-01-29 | 1975-12-16 | Colgate Palmolive Co | Dentifrices |
| US3959458A (en) * | 1973-02-09 | 1976-05-25 | The Procter & Gamble Company | Oral compositions for calculus retardation |
| GB1435624A (en) * | 1973-11-16 | 1976-05-12 | Beecham Group Ltd | Oral hygiene composition |
| GB1514942A (en) * | 1974-09-28 | 1978-06-21 | Beecham Group Ltd | Oral hygiene compositions |
| US4098878A (en) * | 1974-10-29 | 1978-07-04 | Colgate-Palmolive Company | Toothpaste containing milled alpha-alumina trihydrate |
| GB1544537A (en) | 1975-12-12 | 1979-04-19 | Colgate Palmolive Co | Dentifrices and materials useful as dentifrice ingredients |
| US4152419A (en) * | 1977-05-25 | 1979-05-01 | Colgate-Palmolive Company | Dentifrice composition |
| JPS548712A (en) * | 1977-06-13 | 1979-01-23 | Colgate Palmolive Co | Composition for oral cavity |
-
1979
- 1979-12-19 GB GB7943642A patent/GB2068727B/en not_active Expired
-
1980
- 1980-11-19 NZ NZ195585A patent/NZ195585A/en unknown
- 1980-11-24 GR GR63441A patent/GR72833B/el unknown
- 1980-11-26 DE DE19803044448 patent/DE3044448A1/en active Granted
- 1980-11-28 ZW ZW289/80A patent/ZW28980A1/en unknown
- 1980-12-02 AT AT0587680A patent/AT390731B/en not_active IP Right Cessation
- 1980-12-02 ZA ZA00807530A patent/ZA807530B/en unknown
- 1980-12-03 FR FR8025643A patent/FR2471782B1/en not_active Expired
- 1980-12-11 NL NL8006737A patent/NL8006737A/en not_active Application Discontinuation
- 1980-12-12 SE SE8008751A patent/SE448677B/en not_active IP Right Cessation
- 1980-12-12 ZM ZM110/80A patent/ZM11080A1/en unknown
- 1980-12-15 BR BR8008183A patent/BR8008183A/en unknown
- 1980-12-15 IT IT50371/80A patent/IT1188975B/en active
- 1980-12-15 PH PH24984A patent/PH20455A/en unknown
- 1980-12-15 AU AU65392/80A patent/AU536547B2/en not_active Ceased
- 1980-12-15 DK DK533180A patent/DK156616C/en not_active IP Right Cessation
- 1980-12-17 PT PT72217A patent/PT72217A/en unknown
- 1980-12-17 BE BE0/203204A patent/BE886710A/en not_active IP Right Cessation
- 1980-12-18 CA CA000367051A patent/CA1148088A/en not_active Expired
- 1980-12-18 IE IE2669/80A patent/IE51063B1/en not_active IP Right Cessation
- 1980-12-18 ES ES497870A patent/ES8107019A1/en not_active Expired
- 1980-12-18 NO NO803871A patent/NO158204C/en unknown
- 1980-12-19 JP JP18032980A patent/JPS5699408A/en active Granted
- 1980-12-19 CH CH941680A patent/CH644754A5/en not_active IP Right Cessation
- 1980-12-19 AR AR283724A patent/AR223411A1/en active
- 1980-12-22 US US06/219,298 patent/US4357317A/en not_active Expired - Lifetime
- 1980-12-29 IN IN919/DEL/80A patent/IN155160B/en unknown
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