Antimicrobial polymeric biguanide and acidic co-polymer composition and method of use

1. A composition comprising:

(i) an anti-microbial agent comprising a polymeric biguanide, alone or in combination with at least one other microbiologically active component selected from the group consisting of quaternary ammonium compounds, monoquaternary heterocyclic amine salts, urea derivatives, amino compounds, imidazole derivatives, nitrile compounds, tin compounds or complexes, isothiazolin-3-ones, thiazole derivatives, nitro compounds, iodine compounds, aldehyde release agents, thiones, triazine derivatives, oxazolidine and derivatives thereof, furan and derivatives thereof, carboxylic acids and the salts and esters thereof, phenol and derivatives thereof, sulphone derivatives, imides, thioamides, 2-mercapto-pyridine-N-oxide, azole fungicides, strobilurins, amides, carbamates, pyridine derivatives, compounds with active halogen groups, and organometallic compounds;

wherein the polymeric biguanide is a linear polymeric biguanide comprising a mixture of polymer chains in which the individual polymer chains excluding the terminating groups contain at least one recurring unit having two biguanide groups of Formula (4):

wherein d and e represent bridging groups which may be the same or different and in which together the total of the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by d plus the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by e is more than 9 and less than 17; and

(ii) an acidic co-polymer of the Formula (1)

wherein:

[A] is of Formula (9),

[B] is of Formula (10),

L in [B] comprises a group of the Formula:

[C] is of Formula (12),

[G] in [C] is of the Formula:

wherein d′ is 2, 3, 4 or 5;

wherein:

[X] is of Formula (11),

wherein [A], [B] and [C] may occur in any order;

T is a group of the Formula —C(O)OR 6 , wherein R 6 is C 1-10 -alkyl;

L and G each independently is an optionally substituted linking group;

R 1 , R 2 and R 3 are each independently H, C 1-20 -alkyl or C 3-20 -cycloalkyl;

R 4 and R 5 are each independently H or C 1-4 -alkyl;

q is 15 to 1000;

p is 3 to 50;

J is an optionally substituted hydrocarbyl group;

F is an acidic substituent;

b is 0, 1, or 2;

m is 1 to 350;

n is 1 to 75;

v is 1 to 100; and

w is 1 to 4;

provided that at least one of R 4 and R 5 is H and provided that R 1 , R 2 , R 3 , T, L, J and G do not contain a basic group; and

wherein the pka value of the acidic substituent F on the monomer from which [C] is derived is less than 5.5 and wherein acidic substituent [F] comprises a carboxylic acid, a sulphonic acid, a phosphonic acid, or a phosphoric acid.

2. The composition of claim 1 wherein the polymeric biguanide is of Formula (6):

wherein n 1 is from 4 to 20.

3. The composition of claim 1 wherein the acidic co-polymer comprises a cloud point of greater than 15° C.

4. The composition of claim 1 wherein R 1 , R 2 and R 3 are each independently H or —CH 3 .

5. The composition of claim 1 wherein R 4 and R 5 are each independently H.

6. The composition according to claim 1 wherein [J] in [C] is of the Formula:

wherein R 1 , v and [G] are as defined in claim 1 .

7. A composition comprising

(i) an anti-microbial agent comprising a polymeric biguanide wherein the polymeric biguanide is a linear polymeric biguanide comprising a mixture of polymer chains in which the individual polymer chains excluding the terminating groups contain at least one recurring unit having two biguanide groups of Formula (4):

wherein d and e represent bridging groups which may be the same or different and in which together the total of the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by d plus the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by e is more than 9 and less than 17; and

(ii) an acidic co-polymer of the Formula (1);

wherein the acidic co-polymer of Formula (1) comprises [A] of Formula (13),

[B] is of Formula (14), and

[C] is of Formula (15),

[G] in [C] is of the Formula:

wherein d′ is 2, 3, 4 or 5;

wherein:

[X] is of Formula (11),

wherein [A], [B] and [C] may occur in any order;

wherein:

G is an optionally substituted linking group;

R 6 is C 1-10 -alkyl optionally substituted by a ketone, ether, —OH, epoxide, silane or ketoester group; and

R 1 , R 2 and R 3 are each independently H, C 1-20 -alkyl or C 3-20 -cycloalkyl;

R 4 and R 5 are each independently H or C 1-4 -alkyl;

q is 15 to 1000;

p is 3 to 50;

F is an acidic substituent;

b is 0, L or 2;

m is 1 to 350;

n is 1 to 75; and

v is 1 to 100;

provided that at least one of R 4 and R 5 is H and provided that R 1 , R 2 , R 3 , and G do not contain a basic group; and

wherein acidic substituent [F] comprises a carboxylic acid, a sulphonic acid, a phosphonic acid, or a phosphoric acid.

8. The composition of claim 1 wherein the weight ratio of polymeric biguanide to acidic co-polymer is from 100:1 to 1:1000 weight percent.

9. The composition of claim 1 which comprises a pH of from 1 to 12.

10. The composition of claim 1 wherein the anti-microbial agent comprises a polymeric biguanide in combination with a fungicide.

11. A formulation comprising:

(i) a linear polymeric biguanide of claim 1 ; and

(ii) an acidic co-polymer of claim 1 ; and the formulation further comprising

(iii) a carrier.

12. The formulation of claim 11 wherein the carrier is water or a mixture of water and/or a water miscible organic solvent.

13. The formulation of claim 11 which comprises from 0.01 to 5% by weight polymeric biguanide and from 0.01 to 50% by weight acidic co-polymer.

14. The formulation of claim 11 which comprises a pH in the range of from 1 to 12.

15. A formulation comprising:

(i) a linear polymeric biguanide of claim 1 in combination with a fungicide; and

(ii) an acidic co-polymer of claim 1 ; and the formulation further comprising

(iii) a carrier.