Production of aqueous polymer compositions

• US 5,962,571 A
• Filed: 11/01/1996
• Issued: 10/05/1999
• Est. Priority Date: 05/03/1994
• Status: Expired due to Term

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: Zeneca Resins BV
• Inventors: Buckmann, Alfred Jean Paul, Overbeek, Gerardus Cornelis, Smak, Yvonne Wilhelmina
• Primary Examiner(s): REDDICK, MARIE L
• Application Number:
  US08/737,091
• Time in Patent Office: 1,068 Days
• Field of Search: 524/460, 524/507, 524/517, 524/520, 524/521, 524/522, 523/201, 523/403, 523/404, 523/410, 523/411, 523/412, 428/460, 428/462, 428/463, 428/514
• US Class Current: 524/460
• CPC Class Codes: C08F 265/00 Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08G 18/633 onto polymers of compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C09D 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09D151/04, C09D151/06 take precedence
• CPC Class Codes: C09J 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09J151/04, C09J151/06 take precedence
• CPC Class Codes: Y10T 428/31688 Next to aldehyde or ketone condensation product
• CPC Class Codes: Y10T 428/31696 Including polyene monomers [e.g., butadiene, etc.]
• CPC Class Codes: Y10T 428/31699 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31906 Ester, halide or nitrile of addition polymer

Abstract

Process for making organic solvent-free aqueous crosslinkable polymer composition comprising: a) preparing an aqueous solution of an acid-functional oligomer with Tg 10 to 125° C. and having crosslinker functional groups; b) conducting an aqueous emulsion polymerization to make an aqueous emulsion of an olefinic hydrophobic polymer in the presence of the aqueous oligomer solution, the hydrophobic polymer having Tg at least 25° C. below that of the oligomer and optionally crosslinker functional groups, and c) combining with a crosslinking agent reactable with the crosslinker groups of the oligomer and polymer, said composition having Koenig hardness of ≧40 sec and minimum film forming temperature (MFFT) ≦55° C. Also the aqueous composition so formed and its use in various applications. The aqueous composition has excellent properties and in particular an advantageous balance of MFFT and Koenig hardness.

Claims

1. Process for the production of an organic solvent-free aqueous crosslinkable polymer composition useful for coating, which process is organic solvent-free and comprises:

a) preparing an aqueous solution of an acid-functional oligomer built from olefinically unsaturated monomers, said oligomer having a number average molecular weight Mn within the range of from 500 to 50,000 and a glass transition temperature (Tg) within the range of 10 to 125°

C., said oligomer being formed using an organic solvent-free aqueous emulsion or aqueous solution polymerisation process, and said acid functionality by itself or by neutralization rendering the oligomer water-soluble, and said oligomer also having crosslinker functional groups for imparting crosslinkability when the aqueous polymer composition is subsequently dried,

b) conducting an aqueous emulsion polymerisation process to form an aqueous emulsion of a hydrophobic polymer from at least one olefinically unsaturated monomer in the presence of the aqueous solution of the oligomer, said hydrophobic polymer having a Tg which is at least 40°

C. below the Tg of said oligomer, and said hydrophobic polymer optionally having crosslinker functional groups for imparting crosslinkability when the aqueous polymer composition is subsequently dried, and

c) combining the aqueous emulsion from b) with a crosslinking agent by addition of the crosslinking agent after the polymerisation in step b) and/or performing the polymerisation in the presence of the crosslinking agent, said crosslinking agent being reactable with the crosslinker functional groups of the oligomer and (if present) of the hydrophobic polymer on subsequent drying to effect crosslinking, wherein said crosslinking agent is not an agent which effects crosslinking by the formation of ionic bonds,

and wherein further, said polymer composition on drying has a Koenig hardness of at least 40 sec and said polymer composition has a minimum film forming temperature of ≦

55°

C.

2. Process according to claim 1 wherein said oligomer has a number average molecular weight of from 2,000 to 25,000.

3. Process according to claim 1 wherein said oligomer has a Tg within the range of from 50 to 125°

C.

4. Process according to claim 3 wherein said oligomer has a Tg within the range of from 70 to 125°

C.

5. Process according to claim 1 wherein said polymer composition on drying has a Koenig hardness of from 60 to 200 secs.

6. Process according to claim 1 wherein said polymer composition has a minimum film forming temperature of from 0 to 55°

C.

7. Process according to claim 6 wherein said polymer composition has a minimum film forming temperature of from 0 to 30°

C.

8. Process according to claim 1 wherein the resulting composition has Koenig hardness and minimum film forming temperature according to the following empirical relationship:

space="preserve" listing-type="equation">H≧

1.5T+70

where H is Koenig hardness in seconds and T is minimum film forming temperature in °

C.

9. Process according to claim 8 wherein the empirical relationship is:

space="preserve" listing-type="equation">H≧

1.5T+90.

10. Process according to claim 1 wherein said oligomer is completely or partially, dissolved in the aqueous medium in step a).

11. Process according to claim 10 wherein dissolution of the oligomer is effected by neutralization of the acid groups thereof using a base.

12. Process according to claim 1 wherein said oligomer is derived from an olefinically unsaturated monomer system which includes an acid-bearing comonomer(s), or a comonomer(s) bearing an acid-forming group which yields, or is subsequently convertible to, such an acid group, and a comonomer(s) which has functional groups for imparting crosslinkability.

13. Process according to claim 12 wherein the acid bearing monomer(s) is selected from the group consisting of carboxyl-containing olefinically unsaturated monomers.

14. Process according to claim 13 wherein the monomer(s) is selected from the group consisting of carboxyl-functional acrylic monomers.

15. Process according to claim 14 wherein said carboxyl bearing monomer(s) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and fumaric acid.

16. Process according to claim 12 wherein said monomer system from which the oligomer is formed includes a non-acid functional non-crosslinking comonomer(s) selected from the group consisting of acrylate and methacrylate esters;

styrenes, dienes, vinyl esters, nitriles, and olefinically unsaturated halides.

17. Process according to claim 16 wherein said non-acid functional non-crosslinking comonomer(s) is selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobornyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, styrene, alpha-methyl styrene, t-butylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, isoprene and 1,3-butadiene.

18. Process according to claim 12 wherein the functional groups for providing crosslinkability are selected from the group consisting of epoxy, hydroxyl, ketone and aldehyde, groups.

19. Process according to claim 12 wherein said comonomer(s) with functional groups for imparting crosslinkability is (are) selected from the group consisting of glycidyl acrylate or methacrylate, hydroxyethyl methacrylate or acrylate, acrolein, methacrolein, methyl vinyl ketone, acetoacetoxyethyl methacrylate or acrylate and diacetone acrylamide.

20. Process according to claim 12 wherein the acid-functional oligomer is derived from a monomer system comprising 1 to 45 weight % of acid-functional comonomer(s), 0.5 to 20 weight % of crosslinking comonomer (s) and 98.5 to 50 weight % of non-acid functional, non-crosslinking comonomer(s).

21. Process according to claim 20 wherein said oligomer is derived from a monomer system comprising 3 to 30 weight % of acid-functional comonomer(s), 1 to 15 weight % of crosslinking comonomer(s) and 96 to 65 weight % of non-acid functional, non-crosslinking comonomer(s).

22. Process according to claim 20 wherein the acid comonomer(s) is methacrylic acid and/or acrylic acid and the non-acid functional, non-crosslinking comonomer(s) is one or more selected from the group consisting of methyl methacrylate, styrene, ethylacrylate, n-butyl methacrylate and n-butyl acrylate.

23. Process according to claim 20 wherein said oligomer is derived from a monomer system which comprises 3 to 12 weight % of methacrylic acid and/or acrylic acid, 1 to 10 weight % of diacetone acrylamide and/or acetoacetoxyethyl methacrylate, 50 to 90 weight % of methyl methacrylate, 0 to 30 weight % of one or more of ethyl acrylate, n-butyl acrylate or n-butyl methacrylate and 0 to 40 weight % of styrene.

24. Process according to claim 1 wherein the aqueous emulsion polymerisation of step b) is performed using an amount of emulsifying agent(s) newly added for that step (excluding the oligomer) which is less than 0.5 weight % based on the total weight of monomers charged for step b).

25. Process according to claim 1 wherein the only emulsifying agent(s) which may be present (excluding the oligomer itself) is that remaining from the emulsifying agent(s) used in the oligomer polymerisation of step a).

26. Process according to claim 1 wherein the oligomer formed in step a) acts as an emulsifying agent in the polymerisation of step b).

27. Process according to claim 1 wherein the polymerisation processes in steps a) and b) are carried out in the same polymerisation vessel.

28. Process according to claim 1 wherein said hydrophobic polymer is derived from an olefinically unsaturated monomer system which includes a non-acid bearing, non-crosslink monomer(s).

29. Process according to claim 28 wherein said non-acid, non-crosslinking monomer(s) is selected from the group consisting of one or more of acrylate and methacrylate esters, styrenes, dienes, vinyl esters, nitriles, vinyl halides and vinylidene halides.

30. Process according to claim 29 wherein the acrylate and methacrylate esters are normal and branched alkyl esters of C1 to C12 alcohols, the styrenes are styrene, α

-methyl styrene, o-, m- and p- methylstyrene, o-, m- and p-ethyl styrene, p-chlorostyrene, and p-bromostyrene, the dienes are 1,3-butadiene and isoprene, the vinyl ester is vinyl acetate, the vinyl halide is vinyl chloride, and the vinylidene halide is vinylidene chloride.

31. Process according to claim 28 wherein the monomer system used in the preparation of the hydrophobic polymer includes a crosslinking comonomer(s) having a functional group(s) for providing crosslinkability selected from the group consisting of epoxy, hydroxy, ketone and aldehyde groups.

32. Process according to claim 31 wherein said crosslinking comonomers(s) is one or more selected from the group consisting of glycidyl methacrylate or acrylate, hydroxyethyl methacrylate or acrylate, acetoacetoxy methacrylate or acrylate and diacetone acrylamide.

33. Process according to claim 28 wherein the monomer system used for the preparation of the hydrophobic polymer contains less than 5 weight % of any acid-functional comonomer.

34. Process according to claim 33 wherein the monomer system contains no acid-functional comonomer.

35. Process according to claim 1 wherein said hydrophobic polymer is made from a monomer system comprising at least one selected from the group consisting of C1-C10 alkyl methacrylates and C3-C10 alkyl acrylates, and diacetone acrylamide and/or acetoacetoxyethyl methacrylate.

36. Process according to claim 1 wherein said hydrophobic polymer has a number average molecular weight of at least 50,000.

37. Process according to claim 36 wherein the hydrophobic polymer has a number average molecular weight of at least 100,000.

38. Process according to claim 1 wherein the aqueous solution of the oligomer of step a) is admixed with all of the monomers to be used in the formation of the hydrophobic polymer and an otherwise conventional "all-in-one" batch polymerisation (with no further addition of monomer(s)) is carried out to make the hydrophobic polymer.

39. Process according to claim 1 wherein all of the oligomer solution of step a) is present in the polymerisation vessel used to make the hydrophobic polymer prior to the start of polymerisation together with some of the monomer system for the hydrophobic polymer, with the remainder of the monomer system for the hydrophobic polymer being added in one addition after the polymerisation has commenced.

40. Process according to claim 1 wherein all of the oligomer solution of step a) is present in the polymerisation vessel used to make the hydrophobic polymer prior to the start of the polymerisation, and the monomer system for the hydrophobic polymer is split into several equal parts (batches), these parts being added and polymerised consecutive to one another.

41. Process according to claim 1 wherein part (or none) of the monomer system for the hydrophobic polymer is present prior to the start of polymerisation in the polymerisation vessel used to make the hydrophobic polymer and part (or the entire amount) is fed to the reaction medium in the polymerisation vessel during the course of polymerisation.

42. Process according to claim 41 wherein the aqueous oligomer solution of step a) is present in part in the reaction medium for the polymerisation to make the hydrophobic polymer while part of the aqueous oligomer solution is mixed with the entire monomer system for the hydrophobic polymer and the latter fed to the reaction medium in the polymerisation vessel during the polymerisation.

43. Process according to claim 41 wherein the entire oligomer solution of step a) is present in the polymerisation vessel prior to the start of polymerisation and the entire monomer system for the hydrophobic polymer is fed to the vessel during the polymerisation, there being no oligomer present in the monomer feed.

44. Process according to claim 41 wherein all of the aqueous oligomer solution of step a) is present in the polymerisation vessel prior to the start of the polymerisation together with part of the monomer system for the hydrophobic polymer, and the remainder of the monomer system for the hydrophobic polymer fed during polymerisation, there being no oligomer in the feed.

45. Process according to claim 41 wherein part of the oligomer solution of step a) is present in the polymerisation vessel prior to start of the polymerisation to make the hydrophobic polymer together with part of the monomer system for the hydrophobic polymer, and the remainder of the monomer system for the hydrophobic polymer admixed with the remainder of the oligomer solution is fed during polymerisation.

46. Process according to claim 1 wherein the crosslinking agent is selected, depending on the crosslinking functionality in the oligomer and (if present) in the hydrophobic polymer, from the group consisting of a polyisocyanate, melamine, glycoluril, a polyamine, and a polyhydrazide.

47. Process according to claim 1 wherein the ratio of the number of crosslinker groups present in the oligomer and (if employed) in the hydrophobic polymer to the number of reactive groups (for crosslinking purposes) in the crosslinking agent is within the range of from 10/1 to 1/3.

48. Process according to claim 1 wherein the solids content of the resulting aqueous composition is within the range of from 20 to 65 wt % on a total weight basis.

49. Process according to claim 1 wherein the relative amounts of the oligomer and the hydrophobic polymer in the resulting aqueous composition is such that the wt % of the oligomer, based on the wt of the oligomer plus the hydrophobic polymer, is within the range of from 1 to 70 wt %.

50. Aqueous crosslinkable polymer composition which is organic solvent-free and is useful for coating, which composition is produced by a process which is organic solvent-free and comprises:

a) preparing an aqueous solution of an acid-functional oligomer built from olefinically unsaturated monomers, said oligomer having a number average molecular weight Mn within the range of from 500 to 50,000 and a glass transition temperature (Tg) within the range of 10 to 125°

C., said oligomer being formed using an organic solvent-free aqueous emulsion or aqueous solution polymerisation process, and said acid functionality by itself or by neutralization rendering the oligomer water-soluble, and said oligomer also having crosslinker functional groups for imparting crosslinkability when the aqueous polymer composition is subsequently dried,

b) conducting an aqueous emulsion polymerisation process to form an aqueous emulsion of a hydrophobic polymer from at least one olefinically unsaturated monomer in the presence of the aqueous solution of the oligomer, said hydrophobic polymer having a Tg which is at least 40°

C. below the Tg of said oligomer, and said hydrophobic polymer optionally having crosslinker functional groups for imparting crosslinkability when the aqueous polymer composition is subsequently dried, and

c) combining the aqueous emulsion from b) with a crosslinking agent by addition of the crosslinking agent after the polymerisation in step b) and/or performing the polymerisation in the presence of the crosslinking agent, said crosslinking agent being reactable with the crosslinker functional groups of the oligomer and (if present) of the hydrophobic polymer on subsequent drying to effect crosslinking, wherein said crosslinking agent is not an agent which effects crosslinking by the formation of ionic bonds,

and wherein further, said polymer composition on drying has a Koenig hardness of at least 40 sec and said polymer composition has a minimum film forming temperature of ≦

55°

C.

51. Composition according to claim 50 wherein said composition has Koenig hardness and minimum film forming temperature according to the following empirical relationship:

space="preserve" listing-type="equation">H≧

1.5T+70

where H is Koenig hardness in seconds and T is minimum film forming temperature in °

C.

52. Composition according to claim 51 wherein the empirical relationship is:

space="preserve" listing-type="equation">H≧

1.5T+90.

53. A film, polish, varnish, lacquer, paint, ink or adhesive comprising a composition according to claim 50.

54. a composition according to claim 50 deposited as a protective coating on a wood, plastic, paper or metal substrate.