# US 9,433,569 B2 · Dental care products comprising carbonate-substituted fluoro-hydroxyapatite particles

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- Number: US 9,433,569 B2
- Document ID: US9433569B2
- Status: Granted
- Kind: B2
- Application number: 14/122,109
- Filed: 2011-05-26
- Published: 2014-04-10
- Granted: 2016-09-06
- Earliest claimed: 2011-05-26
- Assignees: Coswell S.p.A.
- Applicants: Paolo Gualandi; Andrea Gualandi; Jacopo Gualandi; Ismaela Foltran; Elisabetta Foresti; Marco Lelli; Marco Marchetti; Filippo Pierini; Norberto Roveri; Stefania Vecchiotti; Isidoro Giorgio Lesci
- Inventors: Paolo Gualandi; Andrea Gualandi; Jacopo Gualandi; Ismaela Foltran; Elisabetta Foresti; Marco Lelli; Marco Marchetti; Filippo Pierini; Norberto Roveri; Stefania Vecchiotti; Isidoro Giorgio Lesci
- Web page: https://patentgrep.com/patent/US9433569B2

## CPC

- A61K 8/69: containing fluorine
- A61K 8/27: Zinc; Compounds thereof
- A61Q 11/00: Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/82: by IR- or Raman-data
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- A61Q: SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A dental care product comprising carbonate-substituted fluoro-hydroxyapatite particles having the formula: Ca(10-z-y-m)ZnxSryMm(PO4)(6-z)(CO3)z(OH)2-wFw wherein M is selected from the group comprising Mg, Se, K and mixtures thereof; x is a number comprised between 0 and 0.02; y is a number comprised between 0.0010 and 0.015; m is a number between 0 and 0.5; z is a number comprised between 0.0010 and 0.010 and w is a number comprised between 0.000002 and 0.0001; wherein said fluoro-hydroxyapatite particles have a crystallinity degree CD comprised between 50 and 85%.

## Claims

### Claim 1

A dental care product comprising carbonate-substituted fluoro-hydroxyapatite particles having the formula:
Ca(10-x-y-m)ZnxSryMm(PO4)(6-z)(CO3)z(OH)2-wFw
wherein M is selected from the group consisting of Mg, Se, K and mixtures thereof; x is a number between 0 and 0.02; y is a number between 0.0010 and 0.015; m is a number between 0 and 0.5; z is a number between 0.0010 and 0.010 and w is a number between 0.000002 and 0.0001; and
wherein said fluoro-hydroxyapatite particles have a crystallinity degree (CD) between 50 and 85%.

### Claim 2 (depends on 1)

A product according to claim 1, wherein M is Mg, x, y, z and w are as defined in claim 1 and m is a number between 0.01 and 0.5; and
wherein said fluoro-hydroxyapatite particles have a crystallinity degree (CD) comprised between 55 and 80%.

### Claim 3 (depends on 1)

A product according to claim 1, wherein M is Mgm1Sem2 wherein m1 is a number between 0.01 and 0.5, m2 is a number between 0.001 and 0.5 and m1+m2≦0.5, x, y, z and w are as defined in claim 1; and
wherein said fluoro-hydroxyapatite particles have a crystallinity degree CD comprised between 60 and 75%.

### Claim 4 (depends on 1)

A product according to claim 1, wherein M is Mgm1Sem2Km3 wherein m1 is a number between 0.01 and 0.5, m2 is a number between 0.001 and 0.5, m3 is a number between 0.0005 and 0.5 and m1+m2+m3≦0.5, x, y, z and w are as defined in claim 1; and
wherein said fluoro-hydroxyapatite particles have a crystallinity degree CD comprised between 60 and 80%.

### Claim 5 (depends on 1)

A product according to claim 1, in the form of suspension, oil, gel or solid.

### Claim 6 (depends on 5)

A product according to claim 5, in the form of a suspension including from 1% to 40% by weight of said particles.

### Claim 7 (depends on 6)

A product according to claim 6, having a pH between 6 and 12.

### Claim 8 (depends on 5)

A product according to claim 5, selected from the group consisting of: toothpaste, tooth powder, chewing gum for oral and dental hygiene, ointment for the gums and mouthwash.

### Claim 9

Carbonate-substituted fluoro-hydroxyapatite particles having the formula:
Ca(10-x-y-m)ZnxSryMm(PO4)(6-z)(CO3)z(OH)2-wFw
wherein M is selected from the group consisting of Mg, Se, K and mixtures thereof; x is a number between 0 and 0.02; v is a number between 0.0010 and 0.015; m is number between 0 and 0.05; z is a number between 0.0010 and 0.010; and w is a number between 0.000002 and 0.0001; and wherein said fluoro-hydroxyapatite particles have a crystallinity degree (CD) between 50 and 85%.

### Claim 10 (depends on 9)

A process for manufacturing a dental care product selected from the group consisting of: toothpaste, tooth powder, chewing gum, ointment for the gums, and mouthwash comprising the steps of:
a) providing an aqueous suspension including particles according to claim 9; and
b) mixing said aqueous suspension with other ingredients of the dental care product.

### Claim 11 (depends on 10)

A process for manufacturing a dental care product selected from the group consisting of: toothpaste, tooth powder, chewing gum, ointment for the gums, and mouthwash comprising the steps of:
a′) providing solid particles according to claim 10; and
b′) mixing the solid particles with other ingredients of the dental care product.

### Claim 12 (depends on 10)

A process according to claim 10, wherein said step a) comprises the steps of:
a1) preparing an aqueous solution or suspension comprising a Ca compound, Ca carbonate and optionally a F compound;
b1) adding Sr and optionally Zn and/or a metal M compound selected from Mg, Se, K and mixtures thereof to the aqueous solution or suspension of step a1);
c1) preparing a mixture of phosphoric acid and optionally a F compound;
d1) forming an aqueous suspension of solid particles of a carbonate-substituted fluoro-hydroxyapatite by adding said mixture to the aqueous solution or suspension of step b1), provided that at least one F compound is present in the mixture of step c1) and/or in the aqueous solution or suspension of step b1), while simultaneously agitating the same over a time comprised between 30 minutes and 7 hours while maintaining said solution or suspension at a temperature comprised between 10 and 90° C.; and
e1) agitating a suspension of particles obtained from step d1) over a time comprised between 1 and 48 hours at a temperature comprised between 10° C. and 90° C.

### Claim 13 (depends on 12)

A process according to claim 12, wherein the aqueous suspension obtained from step d1) has a pH comprised between 5 and 13.

### Claim 14 (depends on 12)

A process according to claim 12, wherein said Ca compound is a calcium salt selected from the group consisting of: calcium hydroxide, calcium carbonate, calcium acetate, calcium oxalate, calcium nitrate, and mixtures thereof.

### Claim 15 (depends on 12)

A process according to claim 12, wherein said Zn compound is a zinc salt selected from the group consisting of: zinc carbonate, zinc oxide, and zinc hydroxide, zinc acetate, zinc nitrate, and mixtures thereof.

### Claim 16 (depends on 12)

A process according to claim 12, wherein said F compound is a fluoride salt selected from the group consisting of: sodium fluoride, sodium fluoride phosphate, fluoridric acid, and mixtures thereof.

### Claim 17 (depends on 12)

A process according to claim 12, wherein said Sr compound is a strontium salt selected from the group consisting of: strontium carbonate, strontium oxide, and strontium hydroxide, and mixtures thereof.

### Claim 18 (depends on 12)

A process according to claim 12, wherein said M compound is a metal salt of a compound selected from the group consisting of Mg compound, Se compound, K compound and mixtures thereof.

### Claim 19 (depends on 18)

A process according to claim 18, wherein said Mg compound is a magnesium salt selected from the group consisting of: magnesium carbonate, magnesium oxide, magnesium hydroxide, magnesium acetate, and mixtures thereof.

### Claim 20 (depends on 18)

A process according to claim 18, wherein said Se compound is a selenium salt of a compound selected from the group consisting of: selenium dioxide, selenium trioxide, selenious acid, selenic acid, and mixtures thereof.

### Claim 21 (depends on 18)

A process according to claim 18, wherein said K compound is a potassium salt selected from the group consisting of: potassium carbonate, potassium oxide, potassium hydroxide, potassium nitrate, potassium hydrogen carbonate, potassium acetate, and mixtures thereof.

### Claim 22 (depends on 12)

A process according to claim 12, wherein step c1) is carried out while bubbling air, a CO2-containing gas or a mixture thereof through the aqueous solution or suspension of step a1) and b1).

### Claim 23 (depends on 12)

A process according to claim 12, wherein step c1) is carried out by adding an aqueous solution including PO43− and optionally F− ions to the aqueous solution or suspension of step a1) and b1).

### Claim 24 (depends on 23)

A process according to claim 23, wherein said aqueous solution including PO43− and optionally F− ions further comprises HCO3− ions.

### Claim 25 (depends on 24)

A process according to claim 24, wherein said aqueous solution including HCO3−, PO43− and optionally F− ions is prepared by bubbling air, CO2 or a mixture thereof through water to obtain a solution of carbonic acid and then adding H3PO4 and F compound thereto.

### Claim 26 (depends on 23)

A process according to claim 23, wherein step c1) is carried out by simultaneously adding a first solution including CO32− ions and a second solution containing PO43− and optionally F− ions to the aqueous solution or suspension of a1) and b1).

### Claim 27 (depends on 11, 12)

A process according to claim 11, wherein said step a′) comprises the steps of:
a2) preparing an aqueous suspension of carbonate-substituted fluoro-hydroxyapatite solid particles by a process according to claim 12;
b2) separating the solid particles from the suspension obtained from step a2);
c2) drying the wet solid particles thus obtained.

### Claim 28 (depends on 27)

A process according to claim 27, wherein said separation step b2) is carried out by decantation, centrifugation or filtration.

### Claim 29 (depends on 27)

A process according to claim 27, wherein said drying step c2) is carried out by freeze-drying the wet solid particles at a temperature lower than 0° C. until reaching a constant weight.

### Claim 30 (depends on 27)

A process according to claim 27, further comprising the step of
d2) washing the separated solid particles with water or a basic solution prior to effecting said drying step c2).

### Claim 31 (depends on 10)

A process according to claim 10, wherein mixing step b) is carried out in a mixing apparatus maintained under vacuum.

### Claim 32 (depends on 10)

A process according to claim 10, wherein mixing step b) is carried out by
b1) mixing the aqueous suspension of step a) with other ingredients of the dental care product except for any surfactant;
b2) incorporating at least one surfactant into the mixture thus obtained.

### Claim 33 (depends on 1)

A method of providing at a tooth outer surface a source of F− and Sr++ ions which are locally released at an acidic pH by hydroxyapatite carrier particles, the method comprising contacting the teeth with a dental care product according to claim 1 so as to form on the tooth outer surface a film including said carbonate-substituted fluoro-hydroxyapatite particles.

### Claim 34 (depends on 11)

A process according to claim 11, wherein mixing step b′) is carried out in a mixing apparatus maintained under vacuum.