US3308029A - Dentifrice compositions comprising dicalcium orthophosphate and sodium monofluorophosphate - Google Patents
Dentifrice compositions comprising dicalcium orthophosphate and sodium monofluorophosphate Download PDFInfo
- Publication number
- US3308029A US3308029A US321689A US32168963A US3308029A US 3308029 A US3308029 A US 3308029A US 321689 A US321689 A US 321689A US 32168963 A US32168963 A US 32168963A US 3308029 A US3308029 A US 3308029A
- Authority
- US
- United States
- Prior art keywords
- dicalcium orthophosphate
- sodium monofluorophosphate
- dentifrice compositions
- weight
- monofluorophosphate
- 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 - Lifetime
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Classifications
-
- 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
- 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
Definitions
- compositions containing an alkali 'metal monofluorophosphate as a source of fluorine and dicalcium orthophosphate as the abrasive are surprisingly compatible.
- the present invention is surprising in view of the fact that with practically all other sources of fluorine, dicalcium orthophosphate is one of the least compatible of all known dentifrice abrasives.
- the dicalcium orthophosphate abrasive can be present in the dentifrice compositions of the present invention in either the anhydrous or dihydrate form, it is generally preferred that the dicalcium orthophosphate portion of the dentifrice composition of this invention be largely (i.e., at least about 50 Weight percent) the dihydrate (CaHPO -2H O). Still further preferred are those compositions wherein practically all of the dicalcium orthophosphate is present in the form of the dihydrate.
- the level of the dicalcium orthophosphate in accordance with the present invention, generally can be varied from about 20 to about 60 weight percent of the final toothpaste composition.
- the level of the dicalcium orthophosphate in such toothpaste should be between about 35 and about 50 Weight percent of the toothpaste composition.
- dicalcium orthophosphates for example often up to about 95 weight percent or more, can be utilized, based on the total weight of the final tooth powder composition.
- the dicalcium orthophosphate need not be the only abrasive material in the dentifrice composition of the present invention. Generally, however, it is preferred that dicalcium orthophosphate, in the form of the dihydrate and/ or the anhydrous material, represent at least about half of all of the abrasive materials in the dentifrice compositions of the present invention.
- alkali metal monofluorophosphate preferably sodium monofluorophosphate
- the relative non-toxicity of the monofluorophosphate as compared with simple fluoride salts such as sodium fluoride
- the usual practice of those using dentifrice compositions of the same general type as the compositions of the present invention to clean their teeth (and simultaneously protect their teeth by reducing the incidence of dental caries) generally between about 0.5 and about 2 (and preferably from about 0.7 to about 0.8) weight percent of the alkali metal monofluorophosphate be present in the detifrice compositions of the present invention.
- Toothpastes generally contain, in addition to the abrasive and the fluorine. source, a sweetener such as saccharin; a humectant such as sorbitol and/ or glycerin; a binding agent such as gum tragacanth, Irish moss extract, carboxymethylcellulose, and the very high molecular weight polyethylene oxides; a sudsing agent such as sodium lauryl sulfate or sodium lauryl sarcosinate; and a flavoring agent.
- a sweetener such as saccharin
- a humectant such as sorbitol and/ or glycerin
- a binding agent such as gum tragacanth, Irish moss extract, carboxymethylcellulose, and the very high molecular weight polyethylene oxides
- a sudsing agent such as sodium lauryl sulfate or sodium lauryl sarcosinate
- a flavoring agent such as sodium lauryl sulfate or
- a powder phase is prepared by intermixing 483 parts of the abrasive-monofluorophosphate composition prepared in accordance with the above-described procedure, 1 part of saccharin, and 16 parts of gum tragacanth. These powders are blended together for about 30 minutes. Then, to one third of the resulting blended powder phase in a conventional stainless steel sigma-blade mixer, 165 parts of a mixture containing equal amounts (by weight) of water and glycerin are added very slowly (over a period of about 30 minutes) while the resulting pasty mixture is being agitated. Subsequently, over an additional 30 minute period, the remaining two-thirds of the blended powder phase and 325 parts of the glycerine-water mixture are added to the pasty mixture.
- the resulting pasty mixture is then stirred in the sigma-blade mixer for an additional 30 minutes to assure product uniformity. During the last 10 minutes of this latter period of agitation, 1 part of a flavoring ingredient and 16 parts of sodium lauryl sulfate are mixed into the product.
- the resulting toothpaste product containing about 0.75 weight percent of sodium monofluorophosphate, is then inserted into conventional metal toothpaste tubes, which are subsequently sealed and stored at room temperature. Periodically one of the tubes is opened and analyzed to determine the amount of fluorine remaining in an available (unreacted with the other ingredients so as to remain soluble in the water when 10 parts of the paste are stirred into parts of distilled water at room temperature for about 1 hour) condition.
- a toothpaste formulation such as that prepared in accordance with the foregoing example is found to retain as much as 55 percent of its original available (water-soluble) fluorine.
- a similar toothpaste, prepared in the same manner, but using an equivalent amount (based on F) of stannous fluoride in place of the sodium monofluorophosphate retains, in available form, only about 25 percent of its original fluoride after 168 days of storage at room temperature.
- a formulation, prepared as in the foregoing example, containing calcium pyrophosphate in place of the dicalcium orthophosphate is found to retain only about 22 percent of its original available fluorine after 168 days of storage at room temperature.
- a toothpaste composition containing from about 20% to about 60%, by weight, of an abrasive material and from about 0.2% to about 2.0%, by weight, of sodium monofluorophosphate; said abrasive material consisting of dicalcium orthophosphate and being characterized by having a particle size small enough to pass through a No. 20 mesh U.S. Standard screen.
- a tooth powder composition containing from about 20% to about 95% by Weight of an abrasive material and from about 0.2% to about 2.0% by weight of sodium monofluorophosphate; said abrasive material consisting of dicalcium orthophosphate dihydrate and being characterized by having particles small enough to pass through a No. 200 mesh US Standard screen.
- a dentifrice composition containing from about 20% to about 95% by weight of an abrasive material and from about 0.2% to about 2.0% by weight of sodium monofluorophosphate; said abrasive material consisting of a dicalcium orthophosphate selected from the group consisting of dicalcium orthophosphate dihydrate, anhydrous dicalcium orthophosphate, and mixtures thereof, the particles of said dicalcium orthophosphate being small enough to pass through a No. 200 mesh US. Standard screen.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Cosmetics (AREA)
Description
United States Patent 3,308,029 DENTIFRICE COMPOSITIONS COMPRISING DI- CALCIUM ORTHOPHOSPHATE AND SODIUM MONOFLUOROPHOSPHATE Elerington Saunders, St. Louis, and Thomas Schrff, Clayton, Mo., assignors to Monsanto Company, a corporation of Delaware No Drawing. Filed Nov. 6, 1963, Ser. No. 321,689 4 Claims. (Cl. 167-93) The present invention relates to novel, valuable dentifrice compositions containing, as a source of fluorine, an alkali metal monofluorophosphate.
It has now been discovered that certain compositions containing an alkali 'metal monofluorophosphate as a source of fluorine and dicalcium orthophosphate as the abrasive are surprisingly compatible. The present invention is surprising in view of the fact that with practically all other sources of fluorine, dicalcium orthophosphate is one of the least compatible of all known dentifrice abrasives.
Although the dicalcium orthophosphate abrasive can be present in the dentifrice compositions of the present invention in either the anhydrous or dihydrate form, it is generally preferred that the dicalcium orthophosphate portion of the dentifrice composition of this invention be largely (i.e., at least about 50 Weight percent) the dihydrate (CaHPO -2H O). Still further preferred are those compositions wherein practically all of the dicalcium orthophosphate is present in the form of the dihydrate. In toothpastes, the level of the dicalcium orthophosphate, in accordance with the present invention, generally can be varied from about 20 to about 60 weight percent of the final toothpaste composition. While levels lower than about 20 weight percent can be used, generally at such lower levels of abrasive, cleaning efliciency of the paste drops sharply. Preferably the level of the dicalcium orthophosphate in such toothpaste should be between about 35 and about 50 Weight percent of the toothpaste composition. In tooth powders, generally higher amounts of dicalcium orthophosphates, for example often up to about 95 weight percent or more, can be utilized, based on the total weight of the final tooth powder composition. The dicalcium orthophosphate need not be the only abrasive material in the dentifrice composition of the present invention. Generally, however, it is preferred that dicalcium orthophosphate, in the form of the dihydrate and/ or the anhydrous material, represent at least about half of all of the abrasive materials in the dentifrice compositions of the present invention.
While the use of even very small amounts of alkali metal monofluorophosphate (preferably sodium monofluorophosphate) in the dentifrice compositions of the present invention is beneficial to at least a certain extent, it is generally preferred that at least about 0.2 weight percent of the alkali metal monofluorophosphate be formulated into the dentifrice compositions of the present in vention. For optimum results, however, taking into account the relative cost of the various ingredients, the relative non-toxicity of the monofluorophosphate (as compared with simple fluoride salts such as sodium fluoride), and the usual practice of those using dentifrice compositions of the same general type as the compositions of the present invention to clean their teeth (and simultaneously protect their teeth by reducing the incidence of dental caries), generally between about 0.5 and about 2 (and preferably from about 0.7 to about 0.8) weight percent of the alkali metal monofluorophosphate be present in the detifrice compositions of the present invention.
In the formulation of finished dentifrice compositions containing the dicalcium orthophosphate abrasive-alkali metal monofluorophosphate mixtures of this invention,
practically any of the auxiliary agents that are conveniently utilized in toothpastes and/or tooth powders can be utilized in conjunction with these novel mixtures. Toothpastes, for example, generally contain, in addition to the abrasive and the fluorine. source, a sweetener such as saccharin; a humectant such as sorbitol and/ or glycerin; a binding agent such as gum tragacanth, Irish moss extract, carboxymethylcellulose, and the very high molecular weight polyethylene oxides; a sudsing agent such as sodium lauryl sulfate or sodium lauryl sarcosinate; and a flavoring agent.
' In the following example, all parts are by weight unless otherwise specified.
Example Into a conventional stainless steel powder blending vessel are poured 10,000 parts of 200 mesh dicalcium orthophosphate dihydrate which has been stabilized with a small amount of tetrasodium pyrophospha-te, and 158 parts of '200 mesh sodium monofluorophosphate. The resulting mixture is then blended for a period of about 1 hour. The resulting uniform blend (containing 98.44 weight percent of dicalcium orthophosphate dihydrate and 1.56 weight percent of sodium monofluorophosphate) is then incorporated into a toothpaste composition in the following manner:
A powder phase is prepared by intermixing 483 parts of the abrasive-monofluorophosphate composition prepared in accordance with the above-described procedure, 1 part of saccharin, and 16 parts of gum tragacanth. These powders are blended together for about 30 minutes. Then, to one third of the resulting blended powder phase in a conventional stainless steel sigma-blade mixer, 165 parts of a mixture containing equal amounts (by weight) of water and glycerin are added very slowly (over a period of about 30 minutes) while the resulting pasty mixture is being agitated. Subsequently, over an additional 30 minute period, the remaining two-thirds of the blended powder phase and 325 parts of the glycerine-water mixture are added to the pasty mixture. The resulting pasty mixture is then stirred in the sigma-blade mixer for an additional 30 minutes to assure product uniformity. During the last 10 minutes of this latter period of agitation, 1 part of a flavoring ingredient and 16 parts of sodium lauryl sulfate are mixed into the product. The resulting toothpaste product, containing about 0.75 weight percent of sodium monofluorophosphate, is then inserted into conventional metal toothpaste tubes, which are subsequently sealed and stored at room temperature. Periodically one of the tubes is opened and analyzed to determine the amount of fluorine remaining in an available (unreacted with the other ingredients so as to remain soluble in the water when 10 parts of the paste are stirred into parts of distilled water at room temperature for about 1 hour) condition.
After being stored for a total of about 168 days, a toothpaste formulation such as that prepared in accordance with the foregoing example is found to retain as much as 55 percent of its original available (water-soluble) fluorine. A similar toothpaste, prepared in the same manner, but using an equivalent amount (based on F) of stannous fluoride in place of the sodium monofluorophosphate retains, in available form, only about 25 percent of its original fluoride after 168 days of storage at room temperature. Similarly, a formulation, prepared as in the foregoing example, containing calcium pyrophosphate in place of the dicalcium orthophosphate is found to retain only about 22 percent of its original available fluorine after 168 days of storage at room temperature.
While the foregoing example is directed to a cold procedure for manufacturing the toothpaste, conventional hot methods can also be used successfully to prepare the surprisingly compatible dentifrice compositions of the present invention.
What is claimed is:
1. A toothpaste composition containing from about 20% to about 60%, by weight, of an abrasive material and from about 0.2% to about 2.0%, by weight, of sodium monofluorophosphate; said abrasive material consisting of dicalcium orthophosphate and being characterized by having a particle size small enough to pass through a No. 20 mesh U.S. Standard screen.
2. A tooth powder composition containing from about 20% to about 95% by Weight of an abrasive material and from about 0.2% to about 2.0% by weight of sodium monofluorophosphate; said abrasive material consisting of dicalcium orthophosphate dihydrate and being characterized by having particles small enough to pass through a No. 200 mesh US Standard screen.
3. A dentifrice composition containing from about 20% to about 95% by weight of an abrasive material and from about 0.2% to about 2.0% by weight of sodium monofluorophosphate; said abrasive material consisting of a dicalcium orthophosphate selected from the group consisting of dicalcium orthophosphate dihydrate, anhydrous dicalcium orthophosphate, and mixtures thereof, the particles of said dicalcium orthophosphate being small enough to pass through a No. 200 mesh US. Standard screen.
4. A dentifrice composition as set forth in claim 3 wherein said dicalcium orthophosphate is in the form of the dihydrate.
References Cited by the Examiner LEWIS GOTTS, Primary Examiner.
20 FRANK CACCIAPAGLIA, 111., ELBERT L. ROBERTS,
Examiners.
RICHARD L. HUFF, Assistant Examiner.
Claims (1)
1. A TOOTHPASTE COMPOSITION CONTAINING FROM ABOUT 20% TO ABOUT 60%, BY WEIGHT OF AN ABRASIVE MATERIAL AND FROM ABOUT 0.2% TO ABOUT 2.0%, BY WEIGHT, OF SODIUM MONOFLUOROPHOSPHATE; SAID ABRASIVE MATERIAL CONSISTING OF DICALCIUM ORTHOPHOSPHATE AND BEING CHARACTERIZED BY HAVING A PARTICLE SIZE SMALL ENOUGH TO PASS THROUGH A NO. 200 MESH U.S. STANDARD SCREEN.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US321689A US3308029A (en) | 1963-11-06 | 1963-11-06 | Dentifrice compositions comprising dicalcium orthophosphate and sodium monofluorophosphate |
NL6412842A NL147034C (en) | 1963-11-06 | 1964-11-04 | PROCESS FOR PREPARING A TOOTH CLEANER CONTAINING AN ALKALINE METAL MONOFLUOROPHOSPHATE AND CALCIUM MONO HYDROGEN PHOSPHATE |
DE1964M0063002 DE1492027B2 (en) | 1963-11-06 | 1964-11-05 | TOOTHPASTE CONTAINING SODIUM MONOFLUORPHOSPHATE |
FR993892A FR1426211A (en) | 1963-11-06 | 1964-11-05 | New toothpaste composition and its preparation process |
GB45072/64A GB1089367A (en) | 1963-11-06 | 1964-11-05 | Fluoride containing dentifrice compositions |
NO155469A NO116438B (en) | 1963-11-06 | 1964-11-06 | |
SE13391/64A SE339288B (en) | 1963-11-06 | 1964-11-06 | |
DK547464A DK146954C (en) | 1963-11-06 | 1964-11-06 | DENTAL CONTAINER CONTAINING AN abrasive and an alkali metal monofluorophosphate, as well as a process for its preparation |
BE655416D BE655416A (en) | 1963-11-06 | 1964-11-06 | |
LU47299D LU47299A1 (en) | 1963-11-06 | 1964-11-06 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US321689A US3308029A (en) | 1963-11-06 | 1963-11-06 | Dentifrice compositions comprising dicalcium orthophosphate and sodium monofluorophosphate |
Publications (1)
Publication Number | Publication Date |
---|---|
US3308029A true US3308029A (en) | 1967-03-07 |
Family
ID=23251608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US321689A Expired - Lifetime US3308029A (en) | 1963-11-06 | 1963-11-06 | Dentifrice compositions comprising dicalcium orthophosphate and sodium monofluorophosphate |
Country Status (9)
Country | Link |
---|---|
US (1) | US3308029A (en) |
BE (1) | BE655416A (en) |
DE (1) | DE1492027B2 (en) |
DK (1) | DK146954C (en) |
GB (1) | GB1089367A (en) |
LU (1) | LU47299A1 (en) |
NL (1) | NL147034C (en) |
NO (1) | NO116438B (en) |
SE (1) | SE339288B (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3966901A (en) * | 1970-12-29 | 1976-06-29 | Colgate-Palmolive Company | Dentifrice preparation |
US4108980A (en) * | 1973-01-11 | 1978-08-22 | Colgate-Palmolive Company | Process of preparing materials having calcium and phosphate components |
US4108962A (en) * | 1974-11-30 | 1978-08-22 | Henkel Kommanditgesellschaft Auf Aktien | Process of stabilization of anhydrous dibasic calcium phosphate against fluorine ions with 3-amino-1-hydroxypropane-1,1-diphosphonic acid |
US4117086A (en) * | 1974-11-30 | 1978-09-26 | Henkel Kommanditgesellschaft Auf Aktien | Process of stabilization of dibasic calcium phosphate dihydrate against hydrolysis with 3-amino-1-hydroxypropane-1,1-diphosphonic acid |
US4122151A (en) * | 1974-11-30 | 1978-10-24 | Henkel Kommanditgesellschaft Auf Aktien | Process of stabilization of dibasic calcium phosphate dihydrate against hydrolysis with cyclic aminophosphonic acids |
US4130630A (en) * | 1974-11-30 | 1978-12-19 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Process of stabilization of anhydrous dibasic calcium phosphate against fluorine ions with cyclic aminophosphonic acids |
EP0045826A1 (en) * | 1980-08-12 | 1982-02-17 | Monsanto Company | Dicalcium phosphate dihydrate having improved stability and a method for preparing it |
FR2495467A1 (en) * | 1980-12-05 | 1982-06-11 | Colgate Palmolive Co | TOOTHPASTE COMPOSITION |
US4357317A (en) * | 1979-12-19 | 1982-11-02 | Colgate-Palmolive Company | Dental cream composition |
US4394371A (en) * | 1981-04-07 | 1983-07-19 | Colgate-Palmolive Company | Dentrifrice preparation |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4340583A (en) | 1979-05-23 | 1982-07-20 | J. M. Huber Corporation | High fluoride compatibility dentifrice abrasives and compositions |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2647073A (en) * | 1951-04-13 | 1953-07-28 | Amm I Dent Inc | Ammoniated dentifrice containing anhydrous dicalcium phosphate |
US2773801A (en) * | 1952-07-03 | 1956-12-11 | Colgate Palmolive Co | Dentifrice compositions comprising a normally-solid water soluble condensation product of ethylene glycol and polypropylene glycol |
US2876166A (en) * | 1953-07-08 | 1959-03-03 | Indiana University Foundation | Dentifrice preparations |
US3119743A (en) * | 1959-08-07 | 1964-01-28 | Ericsson Sten Yngve | Alkali metal monofluorophosphate and calcium carbonate dentifrice |
US3227617A (en) * | 1955-04-25 | 1966-01-04 | Colgate Palmolive Co | Fluoride dentifrice composition |
US3227618A (en) * | 1964-03-09 | 1966-01-04 | Colgate Palmolive Co | Dentifrice composition containing sodium monofluorophosphate |
-
1963
- 1963-11-06 US US321689A patent/US3308029A/en not_active Expired - Lifetime
-
1964
- 1964-11-04 NL NL6412842A patent/NL147034C/en not_active IP Right Cessation
- 1964-11-05 GB GB45072/64A patent/GB1089367A/en not_active Expired
- 1964-11-05 DE DE1964M0063002 patent/DE1492027B2/en not_active Ceased
- 1964-11-06 BE BE655416D patent/BE655416A/xx unknown
- 1964-11-06 DK DK547464A patent/DK146954C/en not_active IP Right Cessation
- 1964-11-06 SE SE13391/64A patent/SE339288B/xx unknown
- 1964-11-06 NO NO155469A patent/NO116438B/no unknown
- 1964-11-06 LU LU47299D patent/LU47299A1/xx unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2647073A (en) * | 1951-04-13 | 1953-07-28 | Amm I Dent Inc | Ammoniated dentifrice containing anhydrous dicalcium phosphate |
US2773801A (en) * | 1952-07-03 | 1956-12-11 | Colgate Palmolive Co | Dentifrice compositions comprising a normally-solid water soluble condensation product of ethylene glycol and polypropylene glycol |
US2876166A (en) * | 1953-07-08 | 1959-03-03 | Indiana University Foundation | Dentifrice preparations |
US3227617A (en) * | 1955-04-25 | 1966-01-04 | Colgate Palmolive Co | Fluoride dentifrice composition |
US3119743A (en) * | 1959-08-07 | 1964-01-28 | Ericsson Sten Yngve | Alkali metal monofluorophosphate and calcium carbonate dentifrice |
US3227618A (en) * | 1964-03-09 | 1966-01-04 | Colgate Palmolive Co | Dentifrice composition containing sodium monofluorophosphate |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3966901A (en) * | 1970-12-29 | 1976-06-29 | Colgate-Palmolive Company | Dentifrice preparation |
US4108980A (en) * | 1973-01-11 | 1978-08-22 | Colgate-Palmolive Company | Process of preparing materials having calcium and phosphate components |
US4108962A (en) * | 1974-11-30 | 1978-08-22 | Henkel Kommanditgesellschaft Auf Aktien | Process of stabilization of anhydrous dibasic calcium phosphate against fluorine ions with 3-amino-1-hydroxypropane-1,1-diphosphonic acid |
US4117086A (en) * | 1974-11-30 | 1978-09-26 | Henkel Kommanditgesellschaft Auf Aktien | Process of stabilization of dibasic calcium phosphate dihydrate against hydrolysis with 3-amino-1-hydroxypropane-1,1-diphosphonic acid |
US4122151A (en) * | 1974-11-30 | 1978-10-24 | Henkel Kommanditgesellschaft Auf Aktien | Process of stabilization of dibasic calcium phosphate dihydrate against hydrolysis with cyclic aminophosphonic acids |
US4130630A (en) * | 1974-11-30 | 1978-12-19 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Process of stabilization of anhydrous dibasic calcium phosphate against fluorine ions with cyclic aminophosphonic acids |
US4357317A (en) * | 1979-12-19 | 1982-11-02 | Colgate-Palmolive Company | Dental cream composition |
EP0045826A1 (en) * | 1980-08-12 | 1982-02-17 | Monsanto Company | Dicalcium phosphate dihydrate having improved stability and a method for preparing it |
FR2495467A1 (en) * | 1980-12-05 | 1982-06-11 | Colgate Palmolive Co | TOOTHPASTE COMPOSITION |
US4348382A (en) * | 1980-12-05 | 1982-09-07 | Colgate-Palmolive Company | Dentifrice composition |
US4394371A (en) * | 1981-04-07 | 1983-07-19 | Colgate-Palmolive Company | Dentrifrice preparation |
Also Published As
Publication number | Publication date |
---|---|
DE1492027A1 (en) | 1970-01-15 |
NL147034C (en) | 1982-01-18 |
NO116438B (en) | 1969-03-24 |
DK146954B (en) | 1984-02-27 |
DE1492027B2 (en) | 1977-03-10 |
BE655416A (en) | 1965-05-06 |
SE339288B (en) | 1971-10-04 |
DK146954C (en) | 1984-08-06 |
NL6412842A (en) | 1965-05-07 |
LU47299A1 (en) | 1965-05-06 |
GB1089367A (en) | 1967-11-01 |
NL147034B (en) | 1975-09-15 |
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