CA1145677A - Phosphate buffer in toothpaste with high level of humectant - Google Patents
Phosphate buffer in toothpaste with high level of humectantInfo
- Publication number
- CA1145677A CA1145677A CA000362354A CA362354A CA1145677A CA 1145677 A CA1145677 A CA 1145677A CA 000362354 A CA000362354 A CA 000362354A CA 362354 A CA362354 A CA 362354A CA 1145677 A CA1145677 A CA 1145677A
- Authority
- CA
- Canada
- Prior art keywords
- toothpaste
- water
- fluoride
- humectant
- composition
- 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
Links
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
-
- 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
- A61K8/25—Silicon; Compounds thereof
-
- 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
- A61K2800/52—Stabilizers
Abstract
Abstract Fluoride toothpastes are described which contain a high level of humectant, a silica abrasive and a fluoride ion source and which have superior fluoride and flavor stability. They comprise (A) from about 6% to 45% of a silica dental abrasive; (B) from about 30% to 70% of a humectant; (C) from about 0.01% to 3% of a fluoride ion source; and (D) from about 10% to 45% of water; said composition additionally containing an amount of a phos-phate buEfering agent providing from about 0.1% to 1%
PO4-3, the amount being sufficient to maintain the pH of a 3:1 water/composition weight ratio slurry in the range of about 6.8 to 8Ø
PO4-3, the amount being sufficient to maintain the pH of a 3:1 water/composition weight ratio slurry in the range of about 6.8 to 8Ø
Description
5t~'7~
WILLIAM D. DENNY, JR.
THOMAS A. I~ETZEL
Technical Field This invention relates to novel, high humectant, toothpaste compositions which are exceptionally stable in terms of their ability to provide therapeutic amounts of soluble fluoride for treatment of dental tissue.
For purposes of this invention, the "soluble fluoride"
10 content of any given toothpaste composition refers to the ppm concentration of flucride ion which is found in a supernatant sample centrifuged from a 3:1 by weight slurry of the toothpaste in water (3:1 = water:
toothpaste). The improved fluoride stability is 15 important since fluoride ions are believed to inter-act with dental enamel to reduce the enamel's acid solubility.
It has been postulated that the effectiveness of fluoride toothpastes in providing enamel antisolu-` 20 bility benefits is dependent upon the amount of fluoride ion which is available for uptake by the enamel being treated. It is, of course, therefore desirable to formulate toothpaste products which provide maximum fluoride ion availability in brushing solutions formed 25 therefrom.
Formulation of toothpastes which provide desirablelevels of soluble fluoride is not accomplished without certain difficulties. All fluoride toothpastes tend, upon storage, to lose their capability of providing 30 their theoretical maximum amount of soluble fluoride.
.
:
11 '~S~'7'~t Fluoride ion sources tend to interact with toothpaste impurities and with such toothpaste components as abrasives, buffers, etc. Such interaction diminishes the ability of the fluoride source to provide "soluble 5 fluoride" upon use.
Background Art Toothpastes containing relatively high levels of humectant, a silica abrasive and a fluoride ion source have been disclosed in the art. Included among the 10 references are U.S. Patent 3,538,230, November 3, 1970 to Pader et al; U.S. Patent 3,68~,637, September 5, 1972 to Pader; U.S. Patent 3,711,604, January 16, 1973 to Colodney et al; U.S. Patent 3,911,104, October 7, 1975 to Harrison; U.S. Patent 3,935,306, January 27, 1976 15 to Roberts et al; and U.S. Patent 4,04~,858, August 9, 1977 to Wason. Although these references disclose compositions similar to those of the present invention, they do not suggest the necessity and desirability of keeping the pH within a certain narrow range.
~ccordingly, it is an object of the present inven-tion to provide toothpaste compositions which contain relatively high levels of humectant, silica dental abrasives, a fluoride ion source, a p~ within a certain range and which possess excellent fluoride compatibility.
Disclosure of the Invention The present invention relates to toothpaste composi-tions which exhibit superior fluoride stability. Such compositions comprise a silica abrasive polishing mater-ial, a humectant, a fluoride ion source, preferably a 30 buffering agent and water. Such toothpastes provide a pH of from about 6.8 to 8.0 when slurried with water in a 3:1 water/composition weight ratio.
'7'^~
The silica abrasive polishing materials comprise from about 6% to 45% by weight of the composition. Such abrasives can be any silica material having an average particle size of from about 0.1 to 30 microns.
The humectant comprises from about 30% to 70% by weight of the composition.
The fluoride ion source comprises from about 0.1%
to 3% by weight of the composition.
The buffering agent comprises an amount suf~icient 10 to produce the desired pH, 6~8 to 8.0, preferably 6.9 to 7.3.
The water in the toothpastes herein comprises from about 10% to 45% by weight of the composition De ~ tion of the Invention The toothpaste compositions of the present inven-15 tion comprise a silica dental abrasive, a humectant,a fluoride ion source, preferably a buffering agent and water. Each of these components as well as optional ingredients, composition use and composition preparation are described in detail as follows:
The instant toothpaste compositions contain from about 6% to 45%, preferably from about 10% to 30~, by weight of a silica abrasive polishing material.
Silica dental abrasives of various types can provide 25 the unique benefits of exceptional dental cleaning and polishing performance without unduly abrading tooth enamel or dentin. Silica abrasive materials are also exceptionally compatible with sources of soluble fluoride.
:, 5~7 ,t The silica abrasive polishing material used herein generally has an average particle size ranging between about 0.1 to 30 microns, preferably 5 and 15 microns. The abrasive can be ~recipitated silica or silica gels such as the silica xerogels describecl in Pader et al; U.S. Patent 3,538,230; issued March 2, 1970. Preferred are the silica xerogels marketed under the trademark "Syloid" by the W.
R. Grace & Company, Davison Chemical Division. ~.specially preferred precipitated silica materials are those marketed by the J. M. Huber Coproration under the trademark, "Zeodent", particularly the silica carrying the designation "zeodent 119". The types of silica dental abrasives useful in the toothpastes of the present invention are described in more detail in DiGiulio, U.S. Patent 3,862,307; issued January 21, 1975.
HUMECTANT
Another essential component of the toothpaste com-positions herein is a humectant. The humectant serves to keep the toothpaste compositions from hardening upon exposure to air. Certain humectants can also impart desirable sweetness or flavor to toothpaste compositions.
The humectant, on a pure humectant basis, generally com-prises from about 30% to 70~, pre~erably from about 45%
to 65~, by weight of the toothpaste compositions herein.
Suitable humectants for use in this invention include edible po]yhydric alcohols such as glycerine, sorbitol, xylitol and propylene glycol. Sorbitol is frequently employed as a 70~ aqueous solution known as Sorb ~.
Mixtures of glycerine and sorbitol are especially preferred as the humectant component of the toothpaste compositions herein.
,. .
"
";
~1~5f~7~ .
FLUORIDE ION SOURCE
The fluoride ion source is present at a level of from about 0.01~ to 3~, preferably from about 0.03%
to 1.0%, by weight of the instant compositions. Such fluoride ions combine with dental enamel and thereby reduce enamel solubility in acid. Application of fluoride ions to dental enamel serves to protect teeth against decay.
A wide variety of fluoride ion-yielding materials can be employed as sources of soluble fluoride in the instant compositions. Examples of suitable fluoride ion-yielding materials are found in Briner et al;
U.S. Patent 3,535,421; issued October 20, 1970 and Widder et al; U.S. Patent 3,678,154; issued July 18, 1972. Preferred fluoride ion sources for use herein include sodium fluoride, potassium fluoride and am-monium fluoride. Sodium fluoride is particularly preferred.
Preferably the instan~ toothpaste compositions 20 pro~ide from about 50 ppm to 10,000 ppm, more prefer-ably from about 100 to 3000 ppm, of fluoride ions in the aqueous solutions which contact dental surfaces when the toothpastes oE the present invention are used in the mouth. Such solutions are simulated by preparing 25 3:1 water/toothpaste slurries (by weight) of the tooth-paste compositions herein and by subsequently centrifuging such slurries to obtain an aqueous supernatant. The fluoride ion concentration in such supernatant is taken as a measure of the "soluble fluoride" provided by any 30 given fluoride toothpaste composition.
S~77 BUFFERING AGENT
The buffering agents useful in the present compositions are those which are capable of maintaining the desired pH. Systems based on phosphates or 5 tris(hydroxymethyl)aminomethane are two examples of such agents. Preferred agents are the water-soluble phosphate salts. For purposes of this invention a "water-soluble"salt is one which is soluble in water to the extent of at least 3.0 g/100 cc H2O at 20 C.
The most preferred phosphate salts for use in the present invention are the simple orthophosphate salts. Orthophosphate salts are derived from tribasic orthophosphoric acid of the formula H3PO4. Water soluble sodium, potassium and ammonium salts can be 15 utilized, There are about ten different crystalline sodium orthophosphate salts including the various hydrates.
~ These include, for example, NaH2PO4, ; NaH PO4 H2O' NaH2po4 2H2o, Na2H po4, 2 4 2 20 Na Hpo4~7H2o~ Na2HPO4 12 H2O' Na3P4 2 3 4 2 and mixtures thereof. Preferred sodium orthophosphates include NaH2PO4 H2O~ Na2HPO4 2II2' 3 4 2 mixtures thereof.
Examples of such potassium and ammonium salts 25 which may also be used herein include
WILLIAM D. DENNY, JR.
THOMAS A. I~ETZEL
Technical Field This invention relates to novel, high humectant, toothpaste compositions which are exceptionally stable in terms of their ability to provide therapeutic amounts of soluble fluoride for treatment of dental tissue.
For purposes of this invention, the "soluble fluoride"
10 content of any given toothpaste composition refers to the ppm concentration of flucride ion which is found in a supernatant sample centrifuged from a 3:1 by weight slurry of the toothpaste in water (3:1 = water:
toothpaste). The improved fluoride stability is 15 important since fluoride ions are believed to inter-act with dental enamel to reduce the enamel's acid solubility.
It has been postulated that the effectiveness of fluoride toothpastes in providing enamel antisolu-` 20 bility benefits is dependent upon the amount of fluoride ion which is available for uptake by the enamel being treated. It is, of course, therefore desirable to formulate toothpaste products which provide maximum fluoride ion availability in brushing solutions formed 25 therefrom.
Formulation of toothpastes which provide desirablelevels of soluble fluoride is not accomplished without certain difficulties. All fluoride toothpastes tend, upon storage, to lose their capability of providing 30 their theoretical maximum amount of soluble fluoride.
.
:
11 '~S~'7'~t Fluoride ion sources tend to interact with toothpaste impurities and with such toothpaste components as abrasives, buffers, etc. Such interaction diminishes the ability of the fluoride source to provide "soluble 5 fluoride" upon use.
Background Art Toothpastes containing relatively high levels of humectant, a silica abrasive and a fluoride ion source have been disclosed in the art. Included among the 10 references are U.S. Patent 3,538,230, November 3, 1970 to Pader et al; U.S. Patent 3,68~,637, September 5, 1972 to Pader; U.S. Patent 3,711,604, January 16, 1973 to Colodney et al; U.S. Patent 3,911,104, October 7, 1975 to Harrison; U.S. Patent 3,935,306, January 27, 1976 15 to Roberts et al; and U.S. Patent 4,04~,858, August 9, 1977 to Wason. Although these references disclose compositions similar to those of the present invention, they do not suggest the necessity and desirability of keeping the pH within a certain narrow range.
~ccordingly, it is an object of the present inven-tion to provide toothpaste compositions which contain relatively high levels of humectant, silica dental abrasives, a fluoride ion source, a p~ within a certain range and which possess excellent fluoride compatibility.
Disclosure of the Invention The present invention relates to toothpaste composi-tions which exhibit superior fluoride stability. Such compositions comprise a silica abrasive polishing mater-ial, a humectant, a fluoride ion source, preferably a 30 buffering agent and water. Such toothpastes provide a pH of from about 6.8 to 8.0 when slurried with water in a 3:1 water/composition weight ratio.
'7'^~
The silica abrasive polishing materials comprise from about 6% to 45% by weight of the composition. Such abrasives can be any silica material having an average particle size of from about 0.1 to 30 microns.
The humectant comprises from about 30% to 70% by weight of the composition.
The fluoride ion source comprises from about 0.1%
to 3% by weight of the composition.
The buffering agent comprises an amount suf~icient 10 to produce the desired pH, 6~8 to 8.0, preferably 6.9 to 7.3.
The water in the toothpastes herein comprises from about 10% to 45% by weight of the composition De ~ tion of the Invention The toothpaste compositions of the present inven-15 tion comprise a silica dental abrasive, a humectant,a fluoride ion source, preferably a buffering agent and water. Each of these components as well as optional ingredients, composition use and composition preparation are described in detail as follows:
The instant toothpaste compositions contain from about 6% to 45%, preferably from about 10% to 30~, by weight of a silica abrasive polishing material.
Silica dental abrasives of various types can provide 25 the unique benefits of exceptional dental cleaning and polishing performance without unduly abrading tooth enamel or dentin. Silica abrasive materials are also exceptionally compatible with sources of soluble fluoride.
:, 5~7 ,t The silica abrasive polishing material used herein generally has an average particle size ranging between about 0.1 to 30 microns, preferably 5 and 15 microns. The abrasive can be ~recipitated silica or silica gels such as the silica xerogels describecl in Pader et al; U.S. Patent 3,538,230; issued March 2, 1970. Preferred are the silica xerogels marketed under the trademark "Syloid" by the W.
R. Grace & Company, Davison Chemical Division. ~.specially preferred precipitated silica materials are those marketed by the J. M. Huber Coproration under the trademark, "Zeodent", particularly the silica carrying the designation "zeodent 119". The types of silica dental abrasives useful in the toothpastes of the present invention are described in more detail in DiGiulio, U.S. Patent 3,862,307; issued January 21, 1975.
HUMECTANT
Another essential component of the toothpaste com-positions herein is a humectant. The humectant serves to keep the toothpaste compositions from hardening upon exposure to air. Certain humectants can also impart desirable sweetness or flavor to toothpaste compositions.
The humectant, on a pure humectant basis, generally com-prises from about 30% to 70~, pre~erably from about 45%
to 65~, by weight of the toothpaste compositions herein.
Suitable humectants for use in this invention include edible po]yhydric alcohols such as glycerine, sorbitol, xylitol and propylene glycol. Sorbitol is frequently employed as a 70~ aqueous solution known as Sorb ~.
Mixtures of glycerine and sorbitol are especially preferred as the humectant component of the toothpaste compositions herein.
,. .
"
";
~1~5f~7~ .
FLUORIDE ION SOURCE
The fluoride ion source is present at a level of from about 0.01~ to 3~, preferably from about 0.03%
to 1.0%, by weight of the instant compositions. Such fluoride ions combine with dental enamel and thereby reduce enamel solubility in acid. Application of fluoride ions to dental enamel serves to protect teeth against decay.
A wide variety of fluoride ion-yielding materials can be employed as sources of soluble fluoride in the instant compositions. Examples of suitable fluoride ion-yielding materials are found in Briner et al;
U.S. Patent 3,535,421; issued October 20, 1970 and Widder et al; U.S. Patent 3,678,154; issued July 18, 1972. Preferred fluoride ion sources for use herein include sodium fluoride, potassium fluoride and am-monium fluoride. Sodium fluoride is particularly preferred.
Preferably the instan~ toothpaste compositions 20 pro~ide from about 50 ppm to 10,000 ppm, more prefer-ably from about 100 to 3000 ppm, of fluoride ions in the aqueous solutions which contact dental surfaces when the toothpastes oE the present invention are used in the mouth. Such solutions are simulated by preparing 25 3:1 water/toothpaste slurries (by weight) of the tooth-paste compositions herein and by subsequently centrifuging such slurries to obtain an aqueous supernatant. The fluoride ion concentration in such supernatant is taken as a measure of the "soluble fluoride" provided by any 30 given fluoride toothpaste composition.
S~77 BUFFERING AGENT
The buffering agents useful in the present compositions are those which are capable of maintaining the desired pH. Systems based on phosphates or 5 tris(hydroxymethyl)aminomethane are two examples of such agents. Preferred agents are the water-soluble phosphate salts. For purposes of this invention a "water-soluble"salt is one which is soluble in water to the extent of at least 3.0 g/100 cc H2O at 20 C.
The most preferred phosphate salts for use in the present invention are the simple orthophosphate salts. Orthophosphate salts are derived from tribasic orthophosphoric acid of the formula H3PO4. Water soluble sodium, potassium and ammonium salts can be 15 utilized, There are about ten different crystalline sodium orthophosphate salts including the various hydrates.
~ These include, for example, NaH2PO4, ; NaH PO4 H2O' NaH2po4 2H2o, Na2H po4, 2 4 2 20 Na Hpo4~7H2o~ Na2HPO4 12 H2O' Na3P4 2 3 4 2 and mixtures thereof. Preferred sodium orthophosphates include NaH2PO4 H2O~ Na2HPO4 2II2' 3 4 2 mixtures thereof.
Examples of such potassium and ammonium salts 25 which may also be used herein include
2 4' 2 4~ K2HPO4 2H2' K2HPO4-6H2O' K3PO4-3H O
K PO4-7H2O, K3PO4 9H2O, (NH4)H2PO4, 4 2 4 (NH4)3PO4 and mixtures of these salts.
''~
An especially preferred phosphate salt mixture for use in the toothpastes herein comprises a mixture 2 4 2 3 O4 12H2O. Amounts of buffer to supply from about 0.1% to about 1% PO4 3 in the composition are generally required to provide the desired buffer capacity, The soluble phosphate salts of the present invention are commercially available materials. A more detailed descrpiton of such phosphate salts useful herein can be found in Kirk ~ Othmer, Encyclopedia of Chemical Technology~ Second Edition, Volume 15, Interscience Publishers, Inc. (1968), pp. 232 - 276.
WATER
Water is another essential element of the toothpastes 15 of this invention. Water employed in the preparation of commercially suitable toothpastes should preferably be deionized and free of organic impurities. Water com-prises from about 10~ to 45~, preferably from about 20~ to 353, by weight of the toothpaste compositions herein.
2Q These amounts of water include the free water whichis added plus that which is introduced with other materials.
OPTIONAL INGREDIENTS
~In addition to the above described essential ;25 components, the toothpastes of this invention can contain a variety of optional conventional toothpaste ingre-dients. Such optional ingredients include binders, sudsing agents, flavoring agents, sweetening agents, anticalculus agents, antiplaque agents, coloring agents 30 and pigments.
, ~S~'~t~
A binding agent is preferably present in the pre-sent compositions to provide a desirable consistency.
Such thickening agents include xanthan gum, hydroxy-ethyl cellulose and water-soluble salts of cellulose 5 ethers such as carboxyvinyl polymers of the type sold~
by the B. F. Goodrich Company under the name Carbopol, sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose. Thickeners of this type are described more fully in Unilever, British Specification 10 1,372,382, published October 30, 1974; Salzman, U.S.
Patent 3,506,757, issued April 14, 1970 and Beecham Group Ltd., Belgian Patent 830,375, published December 18, 1975. Natural g~ms such as carrageenan (Irish moss, Viscarin ~ , gum karaya, gum arabic, and gum tragacanth 15 can also be used. Colloidal magnesium aluminum silicate;
Veegum or finely divided silica can be used as part of the thickening agent system. Preferred thickening agents include carboxyvinyl polymers, xanthan gum, carrageenan, sodium carboxymethyl cellulose, sodium 20carboxymethyl hydroxyethyl cellulose and hydroxyethyl cellulose. The most preferred thickener is a carboxy-t- vinyl polymer. Thickening agents in an amount from 0.03 to 5.0~ by weight of the total composition can be used.
Another preferred optional ingredient is a sudsing 25 agent. Suitable sudsing agents are those which are reasonably stable and form suds throughout a wide pH
range, i.e., non-soap anionic, nonionic, cationic, zwitterionic and amphoterlc organic synthetic deter-gents. Sudsing agents of these types are described 30more fully in Agricola et al; U.S. Patent 3,959,458;
issued May 25, 1976 and in Haefele; U.S. Patent 3,937,807;
issued February 10, 1976.
`' .
Anionic sudsing agents useful herein include the water-soluble salts of alkyl sulfates having from 10 to 18 carbon atoms in the alkyl radical and the water-soluble salts of sulfonated monoglycerides of fatty 5 acids having from lO to 18 carbon atoms. Sodium lauryl sulfate and sodium coconut monoglyceride sulfonates are examples of anoinic surfactants of this type.
Mixtures of anionic surfactants can also be employed.
The nonionic sudsing agents which can be used in 10 the toothpastes of the present invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature. Examples of suitable non-15 ionic sudsing agents include the Pluronics~ polyethyleneoxide condensates of alkyl phenols, products derived from the condensation of ethylene oxide with the reac-tion product of propylene oxide and ethylene diamine, ethylene oxide condensates of aliphatic alcohols, long 20 chain tertiary amine oxides, long chain tertiary phos-phine oxides, long chain dialkyl sulfoxides and mix-tures of such materials.
The zwitterionic synthetic sudsing agents useful in the toothpastes of the present invention can be 25 broadly described as derivatives of aliphatic quater-nary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substi-tuents contains from about 8 to 18 carbon atoms and one 30 contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
The cationic sudsing agents useful in the tooth-pastes of the present invention can be broadly defined :
`:
~4~6t~7 as quaternary ammonium compounds having one long alkyl chain containing from about 8 to about 18 carbon atoms such as lauryl trimethylammonium chloride; cetyl pyridinium chloride; cetyl trimethylammonium bromide;
5 di-isobutylphenoxyethyl-dimethylbenzylammonium chloride;
coconutalkyltrimethylammonium nitrite; cetyl pyridinium fluoride; etc. Especially preferred are the quaternary ammonium fluorides described in U.S. Patent 3,535,421, Briner et al, issued October 20, 1970, where said 10 quaternary ammonium fluorides have detergent properties. The cationic sudsing agents can also ~ct as germicides in certain of the toothpastes herein.
The amphoteric sudsing agents useful in the present 15 invention can be broadly described as derivatives of aliphatic secondary and tertiary amines ln which the aliphatic r~dical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains 20 an anionic water-solubilizing group, e.y., carboxylate, sulfonate, sulfate, phosphate, or phosphonate.
The sudsing agent can be present in the toothpaste compositions of this invention in an amount from 0.1 to 6% by weight of the total composition.
Flavoring agents can also be added to the instant compositions. Sui~able flavoring agents include oil of winter~reen, oil of peppermint, oil of spearmint, oil of sassafras, and oil of clove. Sweetening agents which can be used include saccharin, dextrose, levu-30 lose, aspartame, D-tryptophan, dihydrochalcones and sodium cyclamate. Flavoring agents are generally used in toothpastes at levels of from about 0.01% to 2%
by weigh. and sweetening agents at levels of from about 0.05% to about 2% by welght.
., ,, , , ~
~, ~
1~5~7 When wintergreen flavors are used it has heen found that a pH within the range of 6.9 to 7.3 maximizes both fluoride and flavor stability.
Phosphorus-containing anticalculus agents and/or bis-biguanide antiplaque agents can also optionally be added to the toothpastes of this invention. Phosphorus-containing anticalculus agents such as disodium ethane -l-hydroxy-l, l-diphosphonate and related materials are described more fully in McCune et al; U.S. Patent
K PO4-7H2O, K3PO4 9H2O, (NH4)H2PO4, 4 2 4 (NH4)3PO4 and mixtures of these salts.
''~
An especially preferred phosphate salt mixture for use in the toothpastes herein comprises a mixture 2 4 2 3 O4 12H2O. Amounts of buffer to supply from about 0.1% to about 1% PO4 3 in the composition are generally required to provide the desired buffer capacity, The soluble phosphate salts of the present invention are commercially available materials. A more detailed descrpiton of such phosphate salts useful herein can be found in Kirk ~ Othmer, Encyclopedia of Chemical Technology~ Second Edition, Volume 15, Interscience Publishers, Inc. (1968), pp. 232 - 276.
WATER
Water is another essential element of the toothpastes 15 of this invention. Water employed in the preparation of commercially suitable toothpastes should preferably be deionized and free of organic impurities. Water com-prises from about 10~ to 45~, preferably from about 20~ to 353, by weight of the toothpaste compositions herein.
2Q These amounts of water include the free water whichis added plus that which is introduced with other materials.
OPTIONAL INGREDIENTS
~In addition to the above described essential ;25 components, the toothpastes of this invention can contain a variety of optional conventional toothpaste ingre-dients. Such optional ingredients include binders, sudsing agents, flavoring agents, sweetening agents, anticalculus agents, antiplaque agents, coloring agents 30 and pigments.
, ~S~'~t~
A binding agent is preferably present in the pre-sent compositions to provide a desirable consistency.
Such thickening agents include xanthan gum, hydroxy-ethyl cellulose and water-soluble salts of cellulose 5 ethers such as carboxyvinyl polymers of the type sold~
by the B. F. Goodrich Company under the name Carbopol, sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose. Thickeners of this type are described more fully in Unilever, British Specification 10 1,372,382, published October 30, 1974; Salzman, U.S.
Patent 3,506,757, issued April 14, 1970 and Beecham Group Ltd., Belgian Patent 830,375, published December 18, 1975. Natural g~ms such as carrageenan (Irish moss, Viscarin ~ , gum karaya, gum arabic, and gum tragacanth 15 can also be used. Colloidal magnesium aluminum silicate;
Veegum or finely divided silica can be used as part of the thickening agent system. Preferred thickening agents include carboxyvinyl polymers, xanthan gum, carrageenan, sodium carboxymethyl cellulose, sodium 20carboxymethyl hydroxyethyl cellulose and hydroxyethyl cellulose. The most preferred thickener is a carboxy-t- vinyl polymer. Thickening agents in an amount from 0.03 to 5.0~ by weight of the total composition can be used.
Another preferred optional ingredient is a sudsing 25 agent. Suitable sudsing agents are those which are reasonably stable and form suds throughout a wide pH
range, i.e., non-soap anionic, nonionic, cationic, zwitterionic and amphoterlc organic synthetic deter-gents. Sudsing agents of these types are described 30more fully in Agricola et al; U.S. Patent 3,959,458;
issued May 25, 1976 and in Haefele; U.S. Patent 3,937,807;
issued February 10, 1976.
`' .
Anionic sudsing agents useful herein include the water-soluble salts of alkyl sulfates having from 10 to 18 carbon atoms in the alkyl radical and the water-soluble salts of sulfonated monoglycerides of fatty 5 acids having from lO to 18 carbon atoms. Sodium lauryl sulfate and sodium coconut monoglyceride sulfonates are examples of anoinic surfactants of this type.
Mixtures of anionic surfactants can also be employed.
The nonionic sudsing agents which can be used in 10 the toothpastes of the present invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkylaromatic in nature. Examples of suitable non-15 ionic sudsing agents include the Pluronics~ polyethyleneoxide condensates of alkyl phenols, products derived from the condensation of ethylene oxide with the reac-tion product of propylene oxide and ethylene diamine, ethylene oxide condensates of aliphatic alcohols, long 20 chain tertiary amine oxides, long chain tertiary phos-phine oxides, long chain dialkyl sulfoxides and mix-tures of such materials.
The zwitterionic synthetic sudsing agents useful in the toothpastes of the present invention can be 25 broadly described as derivatives of aliphatic quater-nary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substi-tuents contains from about 8 to 18 carbon atoms and one 30 contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
The cationic sudsing agents useful in the tooth-pastes of the present invention can be broadly defined :
`:
~4~6t~7 as quaternary ammonium compounds having one long alkyl chain containing from about 8 to about 18 carbon atoms such as lauryl trimethylammonium chloride; cetyl pyridinium chloride; cetyl trimethylammonium bromide;
5 di-isobutylphenoxyethyl-dimethylbenzylammonium chloride;
coconutalkyltrimethylammonium nitrite; cetyl pyridinium fluoride; etc. Especially preferred are the quaternary ammonium fluorides described in U.S. Patent 3,535,421, Briner et al, issued October 20, 1970, where said 10 quaternary ammonium fluorides have detergent properties. The cationic sudsing agents can also ~ct as germicides in certain of the toothpastes herein.
The amphoteric sudsing agents useful in the present 15 invention can be broadly described as derivatives of aliphatic secondary and tertiary amines ln which the aliphatic r~dical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains 20 an anionic water-solubilizing group, e.y., carboxylate, sulfonate, sulfate, phosphate, or phosphonate.
The sudsing agent can be present in the toothpaste compositions of this invention in an amount from 0.1 to 6% by weight of the total composition.
Flavoring agents can also be added to the instant compositions. Sui~able flavoring agents include oil of winter~reen, oil of peppermint, oil of spearmint, oil of sassafras, and oil of clove. Sweetening agents which can be used include saccharin, dextrose, levu-30 lose, aspartame, D-tryptophan, dihydrochalcones and sodium cyclamate. Flavoring agents are generally used in toothpastes at levels of from about 0.01% to 2%
by weigh. and sweetening agents at levels of from about 0.05% to about 2% by welght.
., ,, , , ~
~, ~
1~5~7 When wintergreen flavors are used it has heen found that a pH within the range of 6.9 to 7.3 maximizes both fluoride and flavor stability.
Phosphorus-containing anticalculus agents and/or bis-biguanide antiplaque agents can also optionally be added to the toothpastes of this invention. Phosphorus-containing anticalculus agents such as disodium ethane -l-hydroxy-l, l-diphosphonate and related materials are described more fully in McCune et al; U.S. Patent
3,488,419, issued January 6, 1970. Bis-biguanide anti-plaque agents such as chlorhexidine (1,6-bis[N5-p-chlorophenyl-nl-biguanido~ hexane), the soluble and insoluble salts thereof and related materials such as 1,2-big(N5-p-trifluoromethylphenyl-Nl-biguanido) ethane are described more fully in Haefele, U.S. Patent 3,934,002, issued January 20, 1976; Haefele, U.S. Patent 3,937,807, issued February 10, 1976; Procter & Gamble, Belgian Patent 843,244, published December 22, 1976 and Procter & Gamble, Belgian Patent 844,764, published January 31, 1977.
If present, the optional anticalculus and/or anti-plaque agents generally comprise from about 0.01~ to 2.5%
by weight of the toothpaste compositions herein.
M~TIIOD OF M~NUFACTUR~
Toothpaste compo.sitions o the present invention are prepared simply by mixing together in any order and by any conventional means the essential and optional components herein. Once prepared, the compositions herein provide a pH of from about 6.8 to 8.0, preferably 6.9 to 7.3, when said compositions are slurried with water in a 3:1 weight ratio of water to composition. Fluoride toothpastes providing pH values within the 6.8 . -7'7 to 8.0 range provide especially effective dental enamel antisolubility benefits compared to toothpastes with pH
values outside this range. Flavoring of toothpastes within this pH range is also comparatively easy.
Toothpastes which provide slurries having pH values within the 6.8 to 8.0 range are especially suitable for soluble fluoride stabilization.
COMPOSITION USE
Toothpaste compositions of the present invention 10 are used in conventional manner. The toothpaste compo-sitions or slurries thereof are brushed onto dental surfaces and subsequently rinsed away.
During use of the toothpaste herein in conventional manner, pastes or slurries generally contact dental sur-15 faces for at least about 30 seconds. More preferablysuch pastes or slurries contact dental surfaces for at least about 60 seconds.
Several representative toothpastes of the present invention are set forth in the following examples. All 20 percentages used herein are by weight unless otherwise designated.
.
:.
. .
' ~5~'î'7 EXAMPLE I
A toothpaste of the present invention having the following composition is formulated:
Sorbitol (70% Aqueous)58.760 5 Glycerine 15.000 NaH2PO4 H2O 0.025 Na2HPO4-2H2O 0.225 Sodium Saccharin 0.250 Syloid 63* 3.000 10 Syloid 74* 13.000 Flavor 0.920 Water 4.061 Sodium Fluoride 0.243 Carbopol 940** 0.250 15 Xanthan Gum 0.200 Sodium Alkyl (C 2) Sulfate (28.8% 4.000 1 Aqueous) Color (1% Aqueous) 0.066 100 . 000 20 *Xerogel silica abrasives - W. R. Grace & Company, Davison Chemical Division *~Carboxyvinyl polymer - B. F. Goodrich Company.
, .
' S~t~7 EXAMPLE II
Another toothpaste of the present invention having the following formula is formulated.
Sorbitol (70% Aqueous) 51.002 5 Sodium Saccharin 0.220 Trisodiwn Phosphate 1.100 Titanium Dioxide 0.600 Water 3.000 Fla~or 1.060 10 Precipitated Silica* 20.000 Glycerine 18.000 Carbopol 940 0.250 Xanthan Gum 0.500 Sodiwn Alkyl (C12) Sulfate (28.8~ Aqueous) ~.000 15 Sodium Fluoride 0.243 Color 0.02S
100. 00 *Supplied by ~. M. Huber Corporation having the designation Zeodent 119.
7~
EXAMPLE III
A third toothpaste of the present invention having the following formula is fonmulated.
Sorbitol (70~ Aqueous) 50.197 5 Sodium Saccharin 0.120 Na P0 12~ 0 1.450 NaH P0 H 0 Titanium Dioxide . 0.700 Precipitated Silica* 20.000 10 Water 3 0OO
Sodium Fluoride 0.243 Glycerine 18.000 Carbcpol 940 0.250 Xanthan Gum 0.500 15 Flavor 0 900 Sodium Alkyl (Cl~) Sulfate (28.8% 4.000 Aqueous) Colo.r (1% Aqueous) 0.050 100 . oo 20 *As in Example II.
.T IS CL~ 3-~h-' , .
:
..
If present, the optional anticalculus and/or anti-plaque agents generally comprise from about 0.01~ to 2.5%
by weight of the toothpaste compositions herein.
M~TIIOD OF M~NUFACTUR~
Toothpaste compo.sitions o the present invention are prepared simply by mixing together in any order and by any conventional means the essential and optional components herein. Once prepared, the compositions herein provide a pH of from about 6.8 to 8.0, preferably 6.9 to 7.3, when said compositions are slurried with water in a 3:1 weight ratio of water to composition. Fluoride toothpastes providing pH values within the 6.8 . -7'7 to 8.0 range provide especially effective dental enamel antisolubility benefits compared to toothpastes with pH
values outside this range. Flavoring of toothpastes within this pH range is also comparatively easy.
Toothpastes which provide slurries having pH values within the 6.8 to 8.0 range are especially suitable for soluble fluoride stabilization.
COMPOSITION USE
Toothpaste compositions of the present invention 10 are used in conventional manner. The toothpaste compo-sitions or slurries thereof are brushed onto dental surfaces and subsequently rinsed away.
During use of the toothpaste herein in conventional manner, pastes or slurries generally contact dental sur-15 faces for at least about 30 seconds. More preferablysuch pastes or slurries contact dental surfaces for at least about 60 seconds.
Several representative toothpastes of the present invention are set forth in the following examples. All 20 percentages used herein are by weight unless otherwise designated.
.
:.
. .
' ~5~'î'7 EXAMPLE I
A toothpaste of the present invention having the following composition is formulated:
Sorbitol (70% Aqueous)58.760 5 Glycerine 15.000 NaH2PO4 H2O 0.025 Na2HPO4-2H2O 0.225 Sodium Saccharin 0.250 Syloid 63* 3.000 10 Syloid 74* 13.000 Flavor 0.920 Water 4.061 Sodium Fluoride 0.243 Carbopol 940** 0.250 15 Xanthan Gum 0.200 Sodium Alkyl (C 2) Sulfate (28.8% 4.000 1 Aqueous) Color (1% Aqueous) 0.066 100 . 000 20 *Xerogel silica abrasives - W. R. Grace & Company, Davison Chemical Division *~Carboxyvinyl polymer - B. F. Goodrich Company.
, .
' S~t~7 EXAMPLE II
Another toothpaste of the present invention having the following formula is formulated.
Sorbitol (70% Aqueous) 51.002 5 Sodium Saccharin 0.220 Trisodiwn Phosphate 1.100 Titanium Dioxide 0.600 Water 3.000 Fla~or 1.060 10 Precipitated Silica* 20.000 Glycerine 18.000 Carbopol 940 0.250 Xanthan Gum 0.500 Sodiwn Alkyl (C12) Sulfate (28.8~ Aqueous) ~.000 15 Sodium Fluoride 0.243 Color 0.02S
100. 00 *Supplied by ~. M. Huber Corporation having the designation Zeodent 119.
7~
EXAMPLE III
A third toothpaste of the present invention having the following formula is fonmulated.
Sorbitol (70~ Aqueous) 50.197 5 Sodium Saccharin 0.120 Na P0 12~ 0 1.450 NaH P0 H 0 Titanium Dioxide . 0.700 Precipitated Silica* 20.000 10 Water 3 0OO
Sodium Fluoride 0.243 Glycerine 18.000 Carbcpol 940 0.250 Xanthan Gum 0.500 15 Flavor 0 900 Sodium Alkyl (Cl~) Sulfate (28.8% 4.000 Aqueous) Colo.r (1% Aqueous) 0.050 100 . oo 20 *As in Example II.
.T IS CL~ 3-~h-' , .
:
..
Claims (7)
1. A toothpaste composition comprising:
(A) from about 6% to 45% of a silica dental abrasive;
(B) from about 30% to 70% of a humectant;
(C) from about 0.01% to 3% of a fluoride ion source; and (D) from about 10% to 45% of water;
said composition additionally containing an amount of a phosphate buffering agent providing from about 0.1% to 1 PO4-3, the amount being sufficient to maintain the pH of a 3:1 water/composition weight ratio slurry in the range of about 6.8 to 8Ø
(A) from about 6% to 45% of a silica dental abrasive;
(B) from about 30% to 70% of a humectant;
(C) from about 0.01% to 3% of a fluoride ion source; and (D) from about 10% to 45% of water;
said composition additionally containing an amount of a phosphate buffering agent providing from about 0.1% to 1 PO4-3, the amount being sufficient to maintain the pH of a 3:1 water/composition weight ratio slurry in the range of about 6.8 to 8Ø
2. A toothpaste composition in accordance with Claim 1 wherein the amount of silica dental abrasive is from about 10% to 30% and the amount of humectant is from about 45%
to 65%.
to 65%.
3. A toothpaste composition in accordance with Claim 2 wherein the fluoride ion source is sodium fluoride.
4. A toothpaste composition in accordance with Claim 3 which contains an additional toothpaste composition component selected from the group consisting of (A) from about 0.1% to 6% of a sudsing agent;
(B) from about 0.01% to 2% of a flavoring agent;
(C) from about 0.05% to 2% of a sweetening agent;
(D) from about 0.03% to 5% of a toothpaste binder; and (E) mixtures of these additional toothpaste composition components.
(B) from about 0.01% to 2% of a flavoring agent;
(C) from about 0.05% to 2% of a sweetening agent;
(D) from about 0.03% to 5% of a toothpaste binder; and (E) mixtures of these additional toothpaste composition components.
5. A toothpaste composition in accordance with Claim 4 wherein:
(A) the sudsing agent is selected from the group consisting of water-soluble salts of alkyl sulfates, water-soluble salts of sulfonated monoglycerides and mixtures thereof;
(B) the humectant is selected from the group consisting of glycerine, sorbitol, xylitol and mixtures thereof; and (C) the silica abrasive is a precipitated silica.
(A) the sudsing agent is selected from the group consisting of water-soluble salts of alkyl sulfates, water-soluble salts of sulfonated monoglycerides and mixtures thereof;
(B) the humectant is selected from the group consisting of glycerine, sorbitol, xylitol and mixtures thereof; and (C) the silica abrasive is a precipitated silica.
6. A toothpaste composition in accordance with Claim 5 wherein the amount of buffering agent is sufficient to maintain the pH in the range of about 6.9 to 7.3.
7. A toothpaste composition in accordance with Claim 6 which in addition contains a flavoring agent containing methyl salicylate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/084,485 US4314990A (en) | 1979-10-15 | 1979-10-15 | Toothpaste compositions |
US84,485 | 1979-10-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1145677A true CA1145677A (en) | 1983-05-03 |
Family
ID=22185254
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000362354A Expired CA1145677A (en) | 1979-10-15 | 1980-10-14 | Phosphate buffer in toothpaste with high level of humectant |
Country Status (5)
Country | Link |
---|---|
US (1) | US4314990A (en) |
JP (1) | JPS5695111A (en) |
CA (1) | CA1145677A (en) |
GR (1) | GR69614B (en) |
PH (1) | PH15450A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5215740A (en) * | 1991-10-25 | 1993-06-01 | Church & Dwight Co., Inc. | Buffering system for anticalculus dentifrices |
Families Citing this family (77)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4381318A (en) * | 1981-01-05 | 1983-04-26 | Ici Americas Inc. | Maltitol containing gel base systems |
US4357314A (en) * | 1981-01-05 | 1982-11-02 | Ici Americas Inc. | Maltitol containing toothpaste |
DE3114492A1 (en) * | 1981-04-10 | 1982-10-28 | Degussa Ag, 6000 Frankfurt | DENTAL CARE |
NO158361C (en) * | 1981-07-03 | 1988-08-31 | Intradal Nv | DENTAL CARE WITH ANTICARIES EFFECT. |
US4448778A (en) * | 1981-08-03 | 1984-05-15 | Ici Americas Inc. | Maltitol containing gel base systems |
GB2109682B (en) * | 1981-11-19 | 1985-09-11 | Colgate Palmolive Co | Stable dentifrice |
US4545979A (en) * | 1982-02-22 | 1985-10-08 | Warner-Lambert Company | Dental hygiene compositions |
US4401648A (en) * | 1982-03-29 | 1983-08-30 | Colgate-Palmolive Company | Dental cream composition |
US4515772A (en) * | 1982-06-22 | 1985-05-07 | The Procter & Gamble Company | Oral compositions |
US4999184A (en) * | 1982-06-22 | 1991-03-12 | The Procter & Gamble Company | Oral compositions |
US4885155A (en) * | 1982-06-22 | 1989-12-05 | The Procter & Gamble Company | Anticalculus compositions using pyrophosphate salt |
US4806339A (en) * | 1982-06-22 | 1989-02-21 | The Procter & Gamble Company | Oral compositions |
US4540576A (en) * | 1982-08-02 | 1985-09-10 | Johnson & Johnson Dental Products Company | Neutral topical sodium fluoride gel |
US4455294A (en) * | 1982-11-17 | 1984-06-19 | Colgate-Palmolive Company | Stable dentifrice containing acidic siliceous polishing agent |
GB8316382D0 (en) * | 1983-06-16 | 1983-07-20 | Beecham Group Plc | Toothpaste |
US4485089A (en) * | 1983-10-17 | 1984-11-27 | Hercules Incorporated | Gel toothpastes |
US4550018A (en) * | 1984-02-22 | 1985-10-29 | Warner-Lambert Company | Dental hygiene compositions |
US4568540A (en) * | 1984-04-18 | 1986-02-04 | Johnson & Johnson | Oral hygiene compositions |
SE453721B (en) * | 1984-11-06 | 1988-02-29 | Georgios Palaghias | SCHOOL SOLUTION CONTAINING PHOSPHATE DONATOR TO PREVENT THE RISE OF ORAL CORROSION OF DENTAL ALLOYS |
IN166518B (en) * | 1985-08-30 | 1990-05-19 | Colgate Palmolive Co | |
US4806340A (en) * | 1985-09-13 | 1989-02-21 | Colgate-Palmolive Company | Anticalculus oral composition |
US5114704A (en) * | 1989-05-30 | 1992-05-19 | Nabisco Brands, Inc. | Raw hide having a coating containing an inorganic pyrophosphate |
US5015485A (en) * | 1989-05-30 | 1991-05-14 | Nabisco Brands, Inc. | Dog biscuits having a coating containing an inorganic pyrophosphate |
US5000943A (en) * | 1989-05-30 | 1991-03-19 | Nabisco Brands, Inc. | Canine biscuits containing an inorganic pyrophosphate |
US5011679A (en) * | 1989-05-30 | 1991-04-30 | Nabisco Brands, Inc. | Raw hide having a coating containing an inorganic pyrophosphate |
US5094870A (en) * | 1989-05-30 | 1992-03-10 | Nabisco Brands, Inc. | Canine biscuits containing an inorganic pyrophosphate |
US5000940A (en) * | 1989-05-30 | 1991-03-19 | Nabisco Brands, Inc. | Devices, compositions and the like having or containing an inorganic pyrophosphate |
US5000973A (en) * | 1989-05-30 | 1991-03-19 | Nabisco Brands, Inc. | Nutritionally-balanced canine biscuits containing an inorganic pyrophosphate |
US5047231A (en) * | 1989-05-30 | 1991-09-10 | Nabisco Brands, Inc. | Raw hide containing an inorganic pyrophosphate |
US5089255A (en) * | 1989-06-26 | 1992-02-18 | Colgate-Palmolive Company | Dental remineralization |
EP0737059A1 (en) * | 1993-12-29 | 1996-10-16 | The Procter & Gamble Company | Tartar control dentifrice composition containing thymol |
US5669942A (en) * | 1994-03-16 | 1997-09-23 | Mccullough; David Keith | Abrasive sanding paste |
US5702686A (en) * | 1995-07-18 | 1997-12-30 | John O. Butler Company | Clear dentrifice gel for interdental brushes |
US6086372A (en) * | 1997-06-04 | 2000-07-11 | Block Drug Company, Inc. | Dental and oral preparation |
AU1949199A (en) * | 1998-01-15 | 1999-08-02 | Block Drug Company Inc., The | Stable dental and oral preparations for removing tobacco tar and common food stains, as well as refreshing the mouth |
US6238648B1 (en) * | 1999-03-25 | 2001-05-29 | The Procter & Gamble Company | Anti-caries oral care compositions and their methods of use |
US7041277B2 (en) * | 2000-03-10 | 2006-05-09 | Cadbury Adams Usa Llc | Chewing gum and confectionery compositions with encapsulated stain removing agent compositions, and methods of making and using the same |
US6562090B1 (en) | 2000-08-28 | 2003-05-13 | Hercules Incorporated | Fluid abrasive suspension for use in dentifrices |
AU2002323135A1 (en) * | 2001-08-14 | 2003-03-03 | Variant Holdings, Llc. | System for marketing goods and services utilizing computerized central and remote facilities |
CN1610533A (en) * | 2002-01-03 | 2005-04-27 | 宝洁公司 | Stable oral compositions comprising casein phosphopeptide complexes and flouride |
US7445769B2 (en) * | 2002-10-31 | 2008-11-04 | Cadbury Adams Usa Llc | Compositions for removing stains from dental surfaces and methods of making and using the same |
US8524198B2 (en) * | 2003-06-20 | 2013-09-03 | Donald W. Bailey | Xylitol dental maintenance system |
US20100158820A1 (en) * | 2003-06-20 | 2010-06-24 | Bailey Donald W | Xylitol dental maintenance system |
US20080317681A1 (en) * | 2003-07-11 | 2008-12-25 | Petros Gebreselassie | Compositions containing a stain removing complex, and methods of making and using the same |
US7390518B2 (en) * | 2003-07-11 | 2008-06-24 | Cadbury Adams Usa, Llc | Stain removing chewing gum composition |
US20060263473A1 (en) * | 2005-05-23 | 2006-11-23 | Cadbury Adams Usa Llc | Compressed delivery system for active components as part of an edible composition |
US8591973B2 (en) * | 2005-05-23 | 2013-11-26 | Kraft Foods Global Brands Llc | Delivery system for active components and a material having preselected hydrophobicity as part of an edible composition |
US8591972B2 (en) * | 2005-05-23 | 2013-11-26 | Kraft Foods Global Brands Llc | Delivery system for coated active components as part of an edible composition |
US20060263474A1 (en) * | 2005-05-23 | 2006-11-23 | Cadbury Adams Usa Llc. | Enhanced flavor-release comestible compositions and methods for same |
US8591974B2 (en) | 2003-11-21 | 2013-11-26 | Kraft Foods Global Brands Llc | Delivery system for two or more active components as part of an edible composition |
US8597703B2 (en) * | 2005-05-23 | 2013-12-03 | Kraft Foods Global Brands Llc | Delivery system for active components as part of an edible composition including a ratio of encapsulating material and active component |
US8389032B2 (en) * | 2005-05-23 | 2013-03-05 | Kraft Foods Global Brands Llc | Delivery system for active components as part of an edible composition having selected particle size |
US8591968B2 (en) * | 2005-05-23 | 2013-11-26 | Kraft Foods Global Brands Llc | Edible composition including a delivery system for active components |
US8389031B2 (en) * | 2005-05-23 | 2013-03-05 | Kraft Foods Global Brands Llc | Coated delivery system for active components as part of an edible composition |
US9271904B2 (en) * | 2003-11-21 | 2016-03-01 | Intercontinental Great Brands Llc | Controlled release oral delivery systems |
US20050112236A1 (en) * | 2003-11-21 | 2005-05-26 | Navroz Boghani | Delivery system for active components as part of an edible composition having preselected tensile strength |
US7641892B2 (en) * | 2004-07-29 | 2010-01-05 | Cadburry Adams USA, LLC | Tooth whitening compositions and delivery systems therefor |
US7955630B2 (en) * | 2004-09-30 | 2011-06-07 | Kraft Foods Global Brands Llc | Thermally stable, high tensile strength encapsulated actives |
US20060068058A1 (en) * | 2004-09-30 | 2006-03-30 | Cadbury Adams Usa Llc | Thermally stable, high tensile strength encapsulation compositions for actives |
US20060263476A1 (en) * | 2004-08-25 | 2006-11-23 | Cadbury Adams Usa, Llc. | Center-filled chewing gum with barrier layer |
US7727565B2 (en) | 2004-08-25 | 2010-06-01 | Cadbury Adams Usa Llc | Liquid-filled chewing gum composition |
US20060068059A1 (en) * | 2004-09-30 | 2006-03-30 | Cadbury Adams Usa Llc | Encapsulated compositions and methods of preparation |
US9198448B2 (en) | 2005-02-07 | 2015-12-01 | Intercontinental Great Brands Llc | Stable tooth whitening gum with reactive ingredients |
US7879376B2 (en) * | 2005-05-23 | 2011-02-01 | Cadbury Adams Usa Llc | Taste potentiator compositions and edible confectionery and chewing gum products containing same |
US7851005B2 (en) * | 2005-05-23 | 2010-12-14 | Cadbury Adams Usa Llc | Taste potentiator compositions and beverages containing same |
US7851006B2 (en) * | 2005-05-23 | 2010-12-14 | Cadbury Adams Usa Llc | Taste potentiator compositions and beverages containing same |
US20070053972A1 (en) * | 2005-09-08 | 2007-03-08 | Cadbury Adams Usa Llc. | Gelatin capsules containing actives |
US20070178188A1 (en) * | 2006-01-27 | 2007-08-02 | Cadbury Adams Usa Llc | Chewing gum compositions including free neotame sweetener compositions |
US20070178187A1 (en) * | 2006-01-27 | 2007-08-02 | Cadbury Adams Usa Llc | Chewing gum compositions including free neotame sweetener compositions |
US20080267891A1 (en) * | 2007-04-30 | 2008-10-30 | Colgate-Palmolive Company | Oral Care Composition To Reduce Or Eliminate Dental Sensitivity |
EP2166871A4 (en) * | 2007-05-14 | 2012-01-25 | Taste potentiator compositions in oral delivery systems | |
SG175785A1 (en) | 2009-05-18 | 2011-12-29 | Colgate Palmolive Co | Oral compositions containing polyguanidinium compounds and methods of manufacture and use thereof |
AR079639A1 (en) | 2009-12-17 | 2012-02-08 | Colgate Palmolive Co | COMPOSITION OF ANTI-EROSIVE TOOTHPASTE |
JP5727517B2 (en) | 2010-01-29 | 2015-06-03 | コルゲート・パーモリブ・カンパニーColgate−Palmolive Company | Oral care products for sensitive enamel care |
CN107569427A (en) * | 2017-10-17 | 2018-01-12 | 贵州云山环保再生循环科技有限公司 | A kind of Traditional Chinese medicine health-care toothpaste of the extract containing Polygonum multiflower knotweed |
CN107753331A (en) * | 2017-10-17 | 2018-03-06 | 贵州云山环保再生循环科技有限公司 | A kind of Traditional Chinese medicine health-care toothpaste containing Aesculus |
EP3946639A4 (en) * | 2019-04-25 | 2023-07-05 | Colgate-Palmolive Company | Oral care compositions and methods of use |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3538230A (en) * | 1966-12-05 | 1970-11-03 | Lever Brothers Ltd | Oral compositions containing silica xerogels as cleaning and polishing agents |
US3551559A (en) * | 1968-07-16 | 1970-12-29 | Lever Brothers Ltd | Process for producing deaerated toothpaste |
US3705940A (en) * | 1969-02-07 | 1972-12-12 | Degussa | Silicic acid-containing dentifrice |
US3689637A (en) * | 1969-07-11 | 1972-09-05 | Lever Brothers Ltd | Dentifrice composition |
US3911104A (en) * | 1970-09-21 | 1975-10-07 | Colgate Palmolive Co | Gel dentifrices |
US3911102A (en) * | 1970-09-21 | 1975-10-07 | Colgate Palmolive Co | Dentifrices |
US3803301A (en) * | 1971-06-03 | 1974-04-09 | Colgate Palmolive Co | Clear toothpastes containing visible agglomerates |
US3711604A (en) * | 1971-07-19 | 1973-01-16 | Colgate Palmolive Co | Fluoride containing transparent dentifrice |
BE789477A (en) * | 1971-10-01 | 1973-01-15 | Colgate Palmolive Co | GAS-FREE TOOTHPASTE MANUFACTURING PROCESS |
GB1400153A (en) * | 1971-10-05 | 1975-07-16 | Unilever Ltd | Tooth-pastes |
GB1400154A (en) * | 1971-10-22 | 1975-07-16 | Unilever Ltd | Toothpaste |
GB1408922A (en) | 1972-02-02 | 1975-10-08 | Blendax Werke Schneider Co | Process and composition for the remineralisation and prevention of demineralisation of human teeth |
US3935306A (en) * | 1972-04-11 | 1976-01-27 | Colgate-Palmolive Company | Toothpaste formulations |
US3929987A (en) * | 1972-07-03 | 1975-12-30 | Colgate Palmolive Co | Toothpaste |
GB1433743A (en) * | 1972-07-21 | 1976-04-28 | Unilever Ltd | Toothpastes |
US3893840A (en) * | 1972-09-06 | 1975-07-08 | Huber Corp J M | Amorphous precipitated siliceous pigments and methods for their production |
US3928541A (en) * | 1972-09-05 | 1975-12-23 | Huber Corp J M | Amorphous precipitated siliceous pigments for cosmetic or dentrifrice use and methods for their production |
US3906090A (en) * | 1972-09-07 | 1975-09-16 | Colgate Palmolive Co | Clear dentifrice |
ZA737495B (en) * | 1972-10-30 | 1975-05-28 | Colgate Palmolive Co | Toothpastes |
US3939262A (en) * | 1974-01-21 | 1976-02-17 | Monsanto Company | Dentifrices |
US4159280A (en) * | 1976-09-15 | 1979-06-26 | J. M. Huber Corporation | Therapeutic dentifrices in unlined container and methods |
US4141969A (en) * | 1977-02-22 | 1979-02-27 | Colgate-Palmolive Company | Dentifrices containing amorphous silica |
GR68943B (en) * | 1977-12-20 | 1982-03-29 | Huber Corp J M |
-
1979
- 1979-10-15 US US06/084,485 patent/US4314990A/en not_active Expired - Lifetime
-
1980
- 1980-10-08 GR GR63082A patent/GR69614B/el unknown
- 1980-10-14 PH PH24722A patent/PH15450A/en unknown
- 1980-10-14 CA CA000362354A patent/CA1145677A/en not_active Expired
- 1980-10-15 JP JP14307180A patent/JPS5695111A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5215740A (en) * | 1991-10-25 | 1993-06-01 | Church & Dwight Co., Inc. | Buffering system for anticalculus dentifrices |
Also Published As
Publication number | Publication date |
---|---|
PH15450A (en) | 1983-01-18 |
US4314990A (en) | 1982-02-09 |
JPS5695111A (en) | 1981-08-01 |
GR69614B (en) | 1982-07-05 |
US4314990B1 (en) | 1991-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1145677A (en) | Phosphate buffer in toothpaste with high level of humectant | |
US4254101A (en) | Toothpaste compositions | |
US4885155A (en) | Anticalculus compositions using pyrophosphate salt | |
US4515772A (en) | Oral compositions | |
US4590066A (en) | Oral compositions | |
US4684518A (en) | Oral compositions | |
EP0297213B1 (en) | Oral treatment and use of an oral composition | |
CA1203754A (en) | Oral hygiene compositions | |
CA2000168C (en) | Oral compositions | |
US3227617A (en) | Fluoride dentifrice composition | |
GB2164256A (en) | Toothpaste compositions | |
US4726943A (en) | Anti-caries composition | |
US4772461A (en) | Oral compositions | |
US4999184A (en) | Oral compositions | |
US4806339A (en) | Oral compositions | |
NZ220602A (en) | Oral compositions containing abrasives, fluoride ions, pyrophosphate and a selected ratio of sodium ions to potassium ions | |
CA1128420A (en) | Methyloxathiazinone dioxide in oral compositions | |
US4455293A (en) | Stable dentifrice containing neutral siliceous polishing agent | |
CA1333885C (en) | Toothpaste | |
GB2204487A (en) | Oral compositions | |
IE41676B1 (en) | Oral hygiene compositions | |
JPS6041047B2 (en) | toothpaste composition | |
WO1998002135A1 (en) | Stabilized stannous-containing compositions for oral care | |
US4455294A (en) | Stable dentifrice containing acidic siliceous polishing agent | |
WO1994000102A1 (en) | Anticalculus compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |