Oral compositions for plaque, caries and calculus retardation with reduced staining tendencies

Claim 2

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU11## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being zinc phenolsulfonate; c. balance, a carrier which is suitable for use in the oral cavity.

Claim 3

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU12## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing about 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of 8-hydroxyquinoline and pharmaceutically acceptable salts of 8-hydroxyquinoline; C. balance, a carrier which is suitable for use in the oral cavity.

Claim 4

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU12## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing about 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of 8-hydroxyquinoline and pharmaceutically acceptable salts of 8-hydroxyquinoline; C. balance, a carrier which is suitable for use in the oral cavity.

Claim 5

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU13## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of: (1) water-soluble pharmaceutically acceptable salts of homopolymers of aliphatic polycarboxylic acids having the following empirical formula: ##EQU14## wherein X", Y", and Z" are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl; at least one of X", Y" and Z" being selected from the group consisting of carboxyl and carboxymethyl, provided that X" and Y" can be carboxymethyl only when Z" is selected from carboxyl and carboxymethyl; wherein only one of X", Y" and Z" can be methyl, and wherein n" is an integer of from 3 to about 5,000;

Claim 6

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU13## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of: (1) water-soluble pharmaceutically acceptable salts of homopolymers of aliphatic polycarboxylic acids having the following empirical formula: ##EQU14## wherein X", Y", and Z" are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl; at least one of X", Y" and Z" being selected from the group consisting of carboxyl and carboxymethyl, provided that X" and Y" can be carboxymethyl only when Z" is selected from carboxyl and carboxymethyl; wherein only one of X", Y" and Z" can be methyl, and wherein n" is an integer of from 3 to about 5,000;

Claim 7

water-soluble pharmaceutically acceptable salts of copolymers of at least two of polycarboxylic acids having the emperical formula of (1); 3. water-soluble, pharmaceutically acceptable salts of copolymers having the following general formula: ##EQU15## wherein each R 11 is selected from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl and carboxyethyl; wherein only one R 11 is methyl; wherein m is at least 45 mole percent of the copolymer; and wherein X", Y", Z" and n" are selected as in (1): C. balance, a carrier which is suitable for use in the oral cavity.

Claim 8

water-soluble pharmaceutically acceptable salts of copolymers of at least two of polycarboxylic acids having the emperical formula of (1); 3. water-soluble, pharmaceutically acceptable salts of copolymers having the following general formula: ##EQU15## wherein each R 11 is selected from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl and carboxyethyl; wherein only one R 11 is methyl; wherein m is at least 45 mole percent of the copolymer; and wherein X", Y", Z" and n" are selected as in (1): C. balance, a carrier which is suitable for use in the oral cavity.

Claim 9

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU16## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms; a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being selected from the group consisting of polyphosphates of the general formula H a +2 P a O 3a +1 where a is an integer of from 2 to about 30 and pharmaceutically acceptable salts thereof; and C. balance, a carrier which is suitable for use in the oral cavity.

Claim 10

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU16## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms; a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being selected from the group consisting of polyphosphates of the general formula H a +2 P a O 3a +1 where a is an integer of from 2 to about 30 and pharmaceutically acceptable salts thereof; and C. balance, a carrier which is suitable for use in the oral cavity.

Claim 11

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU17## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being a pharmaceutically acceptable salt of a rare earth metal. C. balance, a carrier which is suitable for use in the oral cavity.

Claim 12

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU17## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being a pharmaceutically acceptable salt of a rare earth metal. C. balance, a carrier which is suitable for use in the oral cavity.

Claim 13

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU18## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being selected from the group consisting of phytic acid and pharmaceutically acceptable salts thereof; and C. balance, a carrier which is suitable for use in the oral cavity.

Claim 14

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU18## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being selected from the group consisting of phytic acid and pharmaceutically acceptable salts thereof; and C. balance, a carrier which is suitable for use in the oral cavity.

Claim 15

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU19## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of compounds of the following general formulae and pharmaceutically acceptable salts thereof: ##EQU20## wherein R 1 and R 2 are hydrogen or CH 2 OH; n' is an integer of from 3 to 10; R 3 is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, phenyl, naphthyl, phenylethenyl, benzyl, halogen, amino, dimethylamino, diethylamino, N-hydroxy-N-ethylamine, acetylamino, --CH 2 COOH, --CH 2 PO 3 H 2 , --CH(PO 3 H 2 ) (OH) or --CH 2 CH(PO 3 H 2 ) 2 ; and R 4 is hydrogen, lower alkyl, amino, benzyl, halogen, hydroxyl, --CH 2 COOH, --CH 2 PO 3 H 2 , or --CH 2 CH 2 PO 3 H 2 ; ##EQU21## wherein R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each hydrogen or lower alkyl; ##EQU22## wherein n'" is an integer from 3 to 9; ##EQU23## ##EQU24## wherein X'" and Y' are each hydrogen or hydroxy; or the condensation products of ammonia and phosphorus pentoxide, comprising the compounds ##EQU25## ; and C. balance, a carrier which is suitable for use in the oral cavity.

Claim 16

An oral composition effective in inhibiting the formation of plaque, caries and calculus comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU19## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of compounds of the following general formulae and pharmaceutically acceptable salts thereof: ##EQU20## wherein R 1 and R 2 are hydrogen or CH 2 OH; n' is an integer of from 3 to 10; R 3 is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, phenyl, naphthyl, phenylethenyl, benzyl, halogen, amino, dimethylamino, diethylamino, N-hydroxy-N-ethylamine, acetylamino, --CH 2 COOH, --CH 2 PO 3 H 2 , --CH(PO 3 H 2 ) (OH) or --CH 2 CH(PO 3 H 2 ) 2 ; and R 4 is hydrogen, lower alkyl, amino, benzyl, halogen, hydroxyl, --CH 2 COOH, --CH 2 PO 3 H 2 , or --CH 2 CH 2 PO 3 H 2 ; ##EQU21## wherein R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each hydrogen or lower alkyl; ##EQU22## wherein n'" is an integer from 3 to 9; ##EQU23## ##EQU24## wherein X'" and Y' are each hydrogen or hydroxy; or the condensation products of ammonia and phosphorus pentoxide, comprising the compounds ##EQU25## ; and C. balance, a carrier which is suitable for use in the oral cavity.

Claim 17

The composition of claim 7 having a pH within the range of from about 4 to about 9.

Claim 18

The composition of claim 7 containing a watersoluble source of fluoride in a quanity sufficient to provide fluoride in an amount from about 0.0025 to about 5.0% as F - .

Claim 19

The composition of claim 7 containing from about 0.05 to about 1.2% by weight of the bis-biguanide compound and from about 0.01% to about 5% by weight of the anti-calculus compound, and the pH of the composition is from about 6 to about 7.5.

Claim 20

The composition of claim 7 wherein the bis-biguanide compound is [1,6-di(N 1 ,N 1 '-p-chlorophenyldiguanido-N 5 ,N 5 ')hexane]digluconate, and the anti-calculus compound is disodium ethane-1-hydroxy-1,1-diphosphonate.

Claim 21

The composition of claim 7 wherein the composition is a dentifrice, the carrier is an abrasive present at a level of from 31 to 91.6% and the composition additionally contains from about 0.5 to 5.0 % of a sudsing agent.

Claim 22

The composition of claim 7 wherein the bis-biguanide compound is derived from a pharmaceutically acceptable salt selected from the group consisting of the chloride, acetate, and gluconate salts.

Claim 23

The composition of claim 7 wherein A -- (X) z is an ethylhexyl group and n is 6.

Claim 24

The composition of claim 7 wherein A and A' are each p-chlorophenyl groups, z and z' are O, and n is 6.

Claim 25

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU26## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either O or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide or compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being zinc phenolsulfonate.

Claim 26

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU26## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either O or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide or compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being zinc phenolsulfonate.

Claim 27

The process of claim 16 wherein the two compositions are the same composition.

Claim 28

The process of claim 16 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.

Claim 29

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU27## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of 8-hydroxyquinoline and pharmaceutically acceptable salts of 8-hydroxyquinoline.

Claim 30

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU27## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of 8-hydroxyquinoline and pharmaceutically acceptable salts of 8-hydroxyquinoline.

Claim 31

The process of claim 19 wherein the two compositions are the same composition.

Claim 32

The process of claim 19 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.

Claim 33

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU28## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of: (1) water-soluble pharmaceutically acceptable salts of homopolymers of aliphatic polycarboxylic acids having the following empirical formula: ##EQU29## wherein X", Y", and Z" are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl; at least one of X", Y" and Z" being selected from the group consisting of carboxyl and carboxymethyl, provided that X" and Y" can be carboxymethyl only when Z" is selected from carboxyl and carboxymethyl; wherein only one of X", Y" and Z" can be methyl, and wherein n" is an integer of from 3 to about 5,000;

Claim 34

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU28## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of: (1) water-soluble pharmaceutically acceptable salts of homopolymers of aliphatic polycarboxylic acids having the following empirical formula: ##EQU29## wherein X", Y", and Z" are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl; at least one of X", Y" and Z" being selected from the group consisting of carboxyl and carboxymethyl, provided that X" and Y" can be carboxymethyl only when Z" is selected from carboxyl and carboxymethyl; wherein only one of X", Y" and Z" can be methyl, and wherein n" is an integer of from 3 to about 5,000;

Claim 35

water-soluble pharmaceutically acceptable salts of copolymers of at least two of polycarboxylic acids having the emperical formula of (1); 3. water-soluble, pharmaceutically acceptable salts of copolymers having the following general formula: ##EQU30## wherein each R 11 is selcted from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl and carboxyethyl; wherein only one R 11 is methyl; wherein m is at least 45 mole percent of the copolymer; and wherein X", Y", Z" and n"are selected as in (1).

Claim 36

water-soluble pharmaceutically acceptable salts of copolymers of at least two of polycarboxylic acids having the emperical formula of (1); 3. water-soluble, pharmaceutically acceptable salts of copolymers having the following general formula: ##EQU30## wherein each R 11 is selcted from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl and carboxyethyl; wherein only one R 11 is methyl; wherein m is at least 45 mole percent of the copolymer; and wherein X", Y", Z" and n"are selected as in (1).

Claim 37

The process of claim 22 wherein the two compositions are the same composition.

Claim 38

The process of claim 22 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.

Claim 39

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU31## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of polyphosphates of the general formula H a +2 P a O 3a +1 wherein a is an integer of from 2 to about 30 and pharmaceutically acceptable salts thereof.

Claim 40

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU31## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of polyphosphates of the general formula H a +2 P a O 3a +1 wherein a is an integer of from 2 to about 30 and pharmaceutically acceptable salts thereof.

Claim 41

The process of claim 25 wherein the two compositions are the same composition.

Claim 42

The process of claim 25 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.

Claim 43

The process of treating the oral cavity with a composition comprising: a. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU32## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being a pharmaceutically acceptable salt of a rare earth metal.

Claim 44

The process of treating the oral cavity with a composition comprising: a. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU32## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus agent being a pharmaceutically acceptable salt of a rare earth metal.

Claim 45

The process of claim 28 wherein the two compositions are the same composition.

Claim 46

The process of claim 28 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.

Claim 47

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU33## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of phytic acid and pharmaceutically acceptable salts thereof.

Claim 48

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU33## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble salt where such reaction occurs, said anti-calculus compound being selected from the group consisting of phytic acid and pharmaceutically acceptable salts thereof.

Claim 49

The process of claim 31 wherein the two compositions are the same composition.

Claim 50

The process of claim 31 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.

Claim 51

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU34## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble sale where such reaction occurs, said anti-calculus compound being selected from the group consisting of compounds of the following general formulae and pharmaceutically acceptable salts thereof: ##EQU35## wherein R 1 and R 2 are hydrogen or CH 2 OH; n' is an integer of from 3 to 10; R 3 is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, phenyl, naphthyl, phenylethenyl, benzyl, halogen, amino, dimethylamino, diethylamino, N-hydroxy-N-ethylamine, acetylamino, --CH 2 COOH, --CH 2 PO 3 H 2 , --CH(PO 3 H 2 ) (OH) or --CH 2 CH(PO 3 H 2 ) 2 ; and R 4 is hydrogen, lower alkyl, amino, benzyl, halogen, hydroxyl, --CH 2 COOH, --CH 2 PO 3 H 2 , or --CH 2 CH 2 PO 3 H 2 ; ##EQU36## wherein R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each hydrogen or lower alkyl; ##EQU37## wherein n'" is an integer from 3 to 9; ##EQU38## ##EQU39## wherein X'" and Y' are each hydrogen or hydroxy; or the condensation products of ammonia and phosphorous pentoxide, comprising the compounds ##EQU40##

Claim 52

The process of treating the oral cavity with a composition comprising: A. from about 0.01 to about 2.5% by weight of a bis-biguanide compound having the generic formula: ##EQU34## wherein A and A' each represent either (1) a phenyl radical which can contain as a substituent up to two alkyl or alkoxy groups containing from 1 to about 4 carbon atoms, a nitro group, or a halogen atom; (2) an alkyl group containing from 1 to about 12 carbon atoms; or (3) alicyclic groups containing from 4 to about 12 carbon atoms; wherein X and X' each represent an alkylene radical containing from 1 to 3 carbon atoms; wherein z and z' each can be either 0 or 1; wherein R and R' each represent either hydrogen, an alkyl radical containing from 1 to about 12 carbon atoms, or an aralkyl radical containing from 7 to about 12 carbon atoms; wherein n is an integer from 2 to 12 inclusive; and wherein the polymethylene chain (CH 2 ) n can be interrupted by up to 5 ether, thioether, phenyl or naphthyl moieties; or the pharmaceutically acceptable salts thereof; and a composition comprising: B. from about 0.01 to about 10% by weight of an anti-calculus compound in excess over that which reacts with said bis-biguanide compound to form an insoluble sale where such reaction occurs, said anti-calculus compound being selected from the group consisting of compounds of the following general formulae and pharmaceutically acceptable salts thereof: ##EQU35## wherein R 1 and R 2 are hydrogen or CH 2 OH; n' is an integer of from 3 to 10; R 3 is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, phenyl, naphthyl, phenylethenyl, benzyl, halogen, amino, dimethylamino, diethylamino, N-hydroxy-N-ethylamine, acetylamino, --CH 2 COOH, --CH 2 PO 3 H 2 , --CH(PO 3 H 2 ) (OH) or --CH 2 CH(PO 3 H 2 ) 2 ; and R 4 is hydrogen, lower alkyl, amino, benzyl, halogen, hydroxyl, --CH 2 COOH, --CH 2 PO 3 H 2 , or --CH 2 CH 2 PO 3 H 2 ; ##EQU36## wherein R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each hydrogen or lower alkyl; ##EQU37## wherein n'" is an integer from 3 to 9; ##EQU38## ##EQU39## wherein X'" and Y' are each hydrogen or hydroxy; or the condensation products of ammonia and phosphorous pentoxide, comprising the compounds ##EQU40##

Claim 53

The process of claim 34 wherein the two compositions are the same composition.

Claim 54

The process of claim 34 wherein the oral cavity is treated first with the composition containing the bis-biguanide compound and then with the composition containing the anti-calculus compound.