Cyanoacrylate compositions curable to flexible polymeric materials

1. A cyanoacrylate composition comprising:

(i) at least one lower cyanoacrylate monomer component selected from the group consisting of ethyl cyanoacrylate and methoxycyanoacrylate;

(ii) at least one higher cyanoacrylate monomer component in an amount greater than 12% by weight based on the total weight of the combination of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer, and selected from the group consisting of:

n-propyl-cyanoacrylate, iso-propyl cyanoacrylate, n-butylcyanoacrylate, sec-butyl-cyanoacrylate, iso-butyl-cyanoacrylate, tert-butyl-cyanoacrylate, n-pentyl-cyanoacrylate, 1-methyl-butyl-cyanoacrylate, 1-ethyl-propyl-cyanoacrylate, neopentyl-cyanoacrylate, n-hexyl-cyanoacrylate, 1-methyl pentyl-cyanoacrylate, n-heptyl-cyanoacrylate, n-octyl-cyanoacrylate, n-nonyl-cyanoacrylate, n-decyl-cyanoacrylate, n-undecyl-cyanoacrylate, n-dodecyl-cyanoacrylate, cyclohexyl-cyanoacrylate, benzyl-cyanoacrylate, phenyl-cyanoacrylate, tetrahydrofurfuryl-cyanoacrylate, allyl cyanoacrylate, propargyl-cyanoacrylate, 2-butenyl-cyanoacrylate, phenethyl-cyanoacrylate, chloropropyl-cyanoacrylate, ethoxyethyl-cyanoacrylate, ethoxypropyl-cyanoacrylate, ethoxy isopropyl-cyanoacrylate, propoxyethyl-cyanoacrylate, isopropoxyethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, methoxypropyl-cyanoacrylate, methoxy isopropyl-cyanoacrylate, methoxy butyl-cyanoacrylate, propoxymethyl-cyanoacrylate, propoxy ethyl-cyanoacrylate, propoxy propyl-cyanoacrylate, butoxymethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, butoxypropyl-cyanoacrylate, butoxyisopropyl-cyanoacrylate, butoxy butyl-cyanoacrylate, iso-nonyl-cyanoacrylate, iso-decyl-cyanoacrylate, cyclohexyl methyl-cyanoacrylate, naphtyl-cyanoacrylate, 2-(2′-methoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′-ethoxy)-ethoxy ethyl-cyanoacrylate, 2-(2′-propyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′-butyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′-pentyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′-hexyloxy)-ethoxy ethyl-cyanoacrylate, 2-(2′-methoxy)-propyloxy propyl-cyanoacrylate, 2-(2′-ethoxy)-propyloxy propyl-cyanoacrylate, 2-(2′-propyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′-pentyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′-hexyloxy)-propyloxy propyl-cyanoacrylate, 2-(2′-methoxy)-butyloxy butylcyanoacrylate, 2-(2′-ethoxy)-butyloxy butyl-cyanoacrylate, 2-(2′-butyloxy)-butyloxy butyl-cyanoacrylate, 2-(3′-methoxy)-propyloxy ethyl-cyanoacrylate, 2-(3′-methoxy)-butyloxy ethyl-cyanoacrylate, 2-(3′-methoxy)-propyloxy propyl-cyanoacrylate, 2-(3′-methoxy)-butyloxy propyl-cyanoacrylate, 2-(2′-methoxy)-ethoxy propyl-cyanoacrylate, and 2-(2′-methoxy)-ethoxy, butyl-cyanoacrylate;

(iii) at least one plasticiser component comprising at least one ester group containing plasticiser, the plasticiser component being miscible in a mixture of component (i) and component (ii);

the plasticiser component being present in the composition in an amount between about 15 to about 40% by weight of the composition, and the plasticiser component having an Ap/Po ratio in the range of about 1 to less than about 6, provided the plasticiser component does not include pentaerythritoltetrabenzoate as the sole plasticiser.

2. A cyanoacrylate composition comprising:

(i) at least one lower cyanoacrylate monomer component as defined in claim 1 ;

(ii) at least one higher cyanoacrylate monomer component as defined in claim 1 ; and

(iii) at least one plasticiser component comprising at least one ester group containing plasticiser, the plasticiser component being miscible in a mixture of component (i) and component (ii);

the plasticiser component being present in the composition in an amount between about 15 to about 40% by weight of the composition, and the plasticiser having an Ap/Po ratio in the range of about 1.25 to less than about 6 and/or the plasticiser component comprising trimethyl trimellitate.

3. A composition according to claim 2 , wherein the Ap/Po ratio of the plasticiser is in the range of about 1.25 to about 5.

4. A composition according to claim 2 , wherein the plasticiser is present in an amount from about 20 to about 30% by weight of the composition.

5. A composition according to claim 2 , wherein the plasticiser is a member selected from the group consisting of alkyleneglycol diesters of Formula I:

wherein:

each R is independently phenyl or hydroxyphenyl;

R′=—[(CH 2 ) n —O] m —;

n is an integer from 1 to 4; and

m is 1 or 2;

hydroxy carboxylic acid esters wherein the structural formula of the plasticiser contains one or more moieties A or B or C below provided that it contains at least one moiety A and wherein the two remaining free valences are saturated either with —H or —CH 3 :

wherein:

R is a member selected from the group consisting of —CH 3 , —C 2 H 5 , -propyl, -iso-propyl, -butyl, -iso-butyl, -sec-butyl, and -tert-butyl; and

R′ is a member selected from the group consisting of —C(O)H, —C(O)CH 3 , and —C(O)C 2 H 5 , provided that in the case of more than one R group in a molecule, each R is independently selected from —CH 3 , C 2 H 5 , -propyl, -iso-propyl, -butyl, -iso-butyl, -sec-butyl, and -tert-butyl; and

provided that where there is more than one R′, each R′ is independently selected from a member selected from the group consisting of C(O)H, —C(O)CH 3 , and —C(O)C 2 H 5 .

6. A composition according to claim 2 , wherein the plasticiser is an ester of one or more acids selected from the group consisting of isocitric acid, tartaric acid, malic acid, lactic acid, glyceric acid and glycolic acid.

7. A composition according to claim 2 , wherein the plasticiser is a member selected from the group consisting of: trimethyl trimellitate, diethylene glycol dibenzoate, diethyl malonate, triethyl-O-acetyl citrate, benzylbutyl phthalate, dipropylene glycol dibenzoate, diethyl adipate, tributyl-O-acetyl citrate, dimethyl sebacate, and combinations thereof.

8. A composition according to claim 2 , wherein the plasticiser is a member selected from the group consisting of: tributyl-O-acetyl citrate, triethyl-O-acetyl citrate, dipropylene glycol dibenzoate, diethylene glycol dibenzoate and combinations thereof.

9. A composition according to claim 2 , wherein the plasticiser comprises a combination of tributyl-O-acetyl citrate and triethyl-O-acetyl citrate.

10. A composition according to claim 2 , wherein the higher cyanoacrylate monomer is present in an amount of at least about 15% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

11. A composition according to claim 2 , wherein the higher cyanoacrylate monomer is present in an amount within the range from about 15 to about 75% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

12. A composition according to claim 2 , wherein the amount of higher cyanoacrylate monomer is within the range from about 17 to about 70% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

13. A composition according to claim 2 , wherein the amount of higher cyanoacrylate monomer is within the range from about 17 to about 65% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

14. A composition according to claim 2 , wherein the amount of higher cyanoacrylate monomer is within the range from about 17 to about 45% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

15. A composition according to claim 2 , wherein the higher cyanoacrylate monomer is a member selected from the group consisting of n-propyl-cyanoacrylate, iso-propyl cyanoacrylate, n-butyl-cyanoacrylate, sec-butyl-cyanoacrylate, iso-butyl-cyanoacrylate, tert-butyl-cyanoacrylate, n-pentyl-cyanoacrylate, 1-methyl-butyl-cyanoacrylate, 1-ethyl-propyl-cyanoacrylate, neopentyl-cyanoacrylate, n-hexyl-cyanoacrylate, 1-methyl pentyl-cyanoacrylate, n-heptyl-cyanoacrylate, n-octyl-cyanoacrylate, n-nonyl-cyanoacrylate, n-decyl-cyanoacrylate, n-undecyl-cyanoacrylate, n-dodecyl-cyanoacrylate, cyclohexyl-cyanoacrylate, benzyl-cyanoacrylate, phenyl-cyanoacrylate, tetrahydrofurfuryl-cyanoacrylate, allyl cyanoacrylate, propargyl-cyanoacrylate, 2-butenyl-cyanoacrylate, phenethyl-cyanoacrylate, chloropropyl-cyanoacrylate, ethoxyethyl-cyanoacrylate, ethoxypropyl-cyanoacrylate, ethoxy isopropyl-cyanoacrylate, propoxyethyl-cyanoacrylate, isopropoxyethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, methoxypropyl-cyanoacrylate, methoxy isopropyl-cyanoacrylate, methoxy butyl-cyanoacrylate, propoxymethyl-cyanoacrylate, propoxy ethyl-cyanoacrylate, propoxy propyl-cyanoacrylate, butoxymethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, butoxypropyl-cyanoacrylate, butoxyisopropyl-cyanoacrylate, butoxy butyl-cyanoacrylate and combinations thereof.

16. A composition according to claim 2 , wherein the higher cyanoacrylate monomer is a member selected from the group consisting of isopropyl cyanoacrylate, n-butyl cyanoacrylate, sec-butyl cyanoacrylate, n-propyl cyanoacrylate, isobutyl cyanoacrylate, n-hexyl cyanoacrylate, and combinations thereof.

17. A composition according to claim 2 , wherein the lower alkyl cyanoacrylate monomer is present in an amount from about 20 to about 70% by weight based on the total weight of the composition.

18. A reaction product formed by curing of a composition according to claim 2 .

19. A method of production of a composition according to claim 2 comprising the step of admixing the lower cyanoacrylate monomer, the higher cyanoacrylate monomer and the plasticiser under conditions which do not cure the composition.

20. A process of using a composition according to claim 2 to bond substrates together, comprising the steps of;

providing a first substrate;

applying the composition onto a surface of the first substrate; and

mating a second substrate with the composition-coated first substrate to form a bond therebetween after exposure to conditions appropriate to cure the composition.

21. A process of using a composition according to claim 2 to coat an article, comprising the steps of:

providing a substrate; and

applying the composition over at least a portion of the substrate to form a coating thereon after exposure to conditions appropriate to cure the composition.

22. An assembly formed by applying a composition according to claim 2 to at least a portion of a surface of a substrate and bonding a second substrate thereto by mating the substrates under conditions appropriate to cure the composition.

23. A coated article formed by applying a composition according to claim 2 to at least a portion of a surface of the article to form a coating and exposing the composition to conditions appropriate to cure the composition.

24. An article according to claim 23 , wherein the entire surface of the article is coated.

25. A composition according to claim 1 , wherein the Ap/Po ratio of the plasticiser is in the range of about 1.25 to about 5.

26. A composition according to claim 1 , wherein the plasticiser is present in an amount from about 20 to about 30% by weight of the composition.

27. A composition according to claim 1 , wherein the plasticiser is selected from the group consisting of alkyleneglycol diesters of Formula I:

wherein:

each R is independently phenyl or hydroxyphenyl;

R′=—[(CH 2 ) n —O] m —;

n is an integer from 1 to 4; and

m is 1 or 2;

hydroxy carboxylic acid esters wherein the structural formula of the plasticiser contains one or more moieties A or B or C below provided that it contains at least one moiety A and wherein the two remaining free valences are saturated either with —H or —CH 3 :

wherein:

R is a member selected from the group consisting of —CH 3 , —C 2 H 5 , -propyl, -iso-propyl, -butyl, -iso-butyl, -sec-butyl, and -tert-butyl; and

R′ is a member selected from the group consisting of —C(O)H, —C(O)CH 3 , and —C(O)C 2 H 5 , provided that in the case of more than one R group in a molecule, each R is independently selected from the group consisting of —CH 3 , C 2 H 5 , -propyl, -iso-propyl, -butyl, -iso-butyl, -sec-butyl, and -tert-butyl; and provided that where there is more than one R′, each R′ is independently selected from the group consisting of —C(O)H, —C(O)CH 3 , and —C(O)C 2 H 5 .

28. A composition according to claim 1 , wherein the plasticiser is an ester of one or more acids selected from the group consisting of isocitric acid, tartaric acid, malic acid, lactic acid, glyceric acid and glycolic acid.

29. A composition according and claim 1 , wherein the plasticiser is a member selected from the group consisting of: trimethyl trimellitate, diethylene glycol dibenzoate, diethyl malonate, triethyl-O-acetyl citrate, benzylbutyl phthalate, dipropylene glycol dibenzoate, diethyl adipate, tributyl-O-acetyl citrate, dimethyl sebacate, and combinations thereof.

30. A composition according to claim 1 , wherein the plasticiser is a member selected from the group consisting of: tributyl-O-acetyl citrate, triethyl-O-acetyl citrate, dipropylene glycol dibenzoate, diethylene glycol dibenzoate and combinations thereof.

31. A composition according to claim 1 , wherein the plasticiser component comprises a combination of tributyl-O-acetyl citrate and triethyl-O-acetyl citrate.

32. A composition according to claim 1 , wherein the higher cyanoacrylate monomer is present in an amount of at least about 15% by weight based on the combined weight of the lower cyanoacrylate monomer component and the higher cyanoacrylate monomer.

33. A composition according to claim 1 , wherein the higher cyanoacrylate momomer is present in an amount within the range from about 15 to about 75% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

34. A composition according to claim 1 , wherein the amount of higher cyanoacrylate monomer is within the range from about 17 to about 70% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

35. A composition according to claim 1 , wherein the amount of higher cyanoacrylate monomer is within the range from about 17 to about 65% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

36. A composition according to claim 1 , wherein the amount of higher cyanoacrylate monomer is within the range from about 17 to about 45% by weight based on the combined weight of the lower cyanoacrylate monomer and the higher cyanoacrylate monomer.

37. A composition according to claim 1 , wherein the higher cyanoacrylate monomer is a member selected from the group consisting of n-propyl-cyanoacrylate, iso-propyl cyanoacrylate, n-butyl-cyanoacrylate, sec-butyl-cyanoacrylate, iso-butyl-cyanoacrylate, tert-butyl-cyanoacrylate, n-pentyl-cyanoacrylate, 1-methyl-butyl-cyanoacrylate, 1-ethyl-propyl-cyanoacrylate, neopentyl-cyanoacrylate, n-hexyl-cyanoacrylate, 1-methyl pentyl-cyanoacrylate, n-heptyl-cyanoacrylate, n-octyl-cyanoacrylate, n-nonyl-cyanoacrylate, n-decyl-cyanoacrylate, n-undecyl-cyanoacrylate, n-dodecyl-cyanoacrylate, cyclohexyl-cyanoacrylate, benzyl-cyanoacrylate, phenyl-cyanoacrylate, tetrahydrofurfuryl-cyanoacrylate, allyl cyanoacrylate, propargyl-cyanoacrylate, 2-butenyl-cyanoacrylate, phenethyl-cyanoacrylate, chloropropyl-cyanoacrylate, ethoxyethyl-cyanoacrylate, ethoxypropyl-cyanoacrylate, ethoxy isopropyl-cyanoacrylate, propoxyethyl-cyanoacrylate, isopropoxyethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, methoxypropyl-cyanoacrylate, methoxy isopropyl-cyanoacrylate, methoxy butyl-cyanoacrylate, propoxymethyl-cyanoacrylate, propoxy ethyl-cyanoacrylate, propoxy propyl-cyanoacrylate, butoxymethyl-cyanoacrylate, butoxyethyl-cyanoacrylate, butoxypropyl-cyanoacrylate, butoxyisopropyl-cyanoacrylate, butoxy butyl-cyanoacrylate and combinations thereof.

38. A composition according to claim 1 , wherein the higher cyanoacrylate monomer is a member selected from the group consisting of isopropyl cyanoacrylate, n-butyl cyanoacrylate, sec-butyl cyanoacrylate, n-propyl cyanoacrylate, isobutyl cyanoacrylate, n-hexyl cyanoacrylate, and combinations thereof.

39. A composition according to claim 1 , wherein the lower alkyl cyanoacrylate monomer is present in an amount from about 20 to about 70% by weight based on the total weight of the composition.

40. A reaction product formed by curing of a composition according to claim 1 .

41. A method of production of a composition according to claim 1 comprising the step of admixing the lower cyanoacrylate component, the higher cyanoacrylate component and the plasticiser component under conditions which do not cure the composition.

42. A process of using a composition according to claim 1 to bond substrates together, comprising the steps of:

providing a first substrate;

applying the composition onto a surface of the first substrate; and

mating a second substrate with the composition-coated first substrate to form a bond therebetween after exposure to conditions appropriate to cure the composition.

43. A process of using a composition according to claim 1 to coat an article, comprising the steps of:

providing a substrate; and

applying the composition over at least a portion of the substrate to form a coating thereon after exposure to conditions appropriate to cure the composition.

44. An assembly formed by applying a composition according to claim 1 to at least a portion of a surface of a substrate and bonding a second substrate thereto by mating the substrates under conditions appropriate to cure the composition.

45. A coated article formed by applying a composition according to claim 1 to at least a portion of a surface of the article to form a coating and exposing the composition to conditions appropriate to cure the composition.