Fluoroacrylate-multifunctional acrylate copolymer compositions

• US 7,345,123 B2
• Filed: 12/28/2004
• Issued: 03/18/2008
• Est. Priority Date: 12/28/2004
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Moore, George G. I., Qiu, Zai-Ming, Kumar, Ramesh C., Clark, John C.
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): Bernshteyn; M.
• Application Number:
  US11/027,612
• Publication Number:
  US 20060142519A1
• Time in Patent Office: 1,176 Days
• Field of Search: 526/242, 526/286, 526/319, 526/285, 528/28, 528/70, 528/374
• US Class Current: 526/242
• CPC Class Codes: C08F 220/38 Esters containing sulfur
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 442/2311 Coating or impregnation is a lubricant or a surface friction reducing agent other than specified as improving the "hand" of the fabric or increasing the softness thereof
• CPC Class Codes: Y10T 442/232 Fluorocarbon containing
• CPC Class Codes: Y10T 442/2754 Pressure-sensitive adhesive

Abstract

A composition comprises a copolymer comprising repeating units derived from at least one co-reactant comprising two or more acrylate groups and repeating units derived from a fluoroacrylate comprising the reaction product of:

• • (a) at least one fluorochemical alcohol represented by the formula:
    C₄F₉—X—OH
  • wherein:

• • • R=hydrogen or an alkyl group of 1 to 4 carbon atoms,
    • m=2 to 8,
    • R_f=C_nF_2n+1,
    • n=1 to 5,
    • y 32 0 to 6, and
    • q=1 to 8;
  • (b) at least one unbranched symmetric diisocyanate; and
  • (c) at least one hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer having 2 to about 30 carbon atoms in its alkylene portion;
    wherein the composition is coatable.

Claims

1. A composition comprising a copolymer comprising repeating units derived from at least one co-reactant comprising two or more acrylate groups and repeating units derived from a fluoroacrylate comprising the reaction product of:

(a) at least one fluorochemical alcohol represented by the formula;

C₄F₉—

X—

OH

wherein;

2. The composition of claim 1 wherein the weight ratio of co-reactant to fluoroacrylate is about 35:

65 or less.

3. The composition of claim 2 wherein the weight ratio of co-reactant to fluoroacrylate is about 20:

80 or less.

4. The composition of claim 1 wherein the co-reactant is a tri(meth)acrylate or a di(meth)acrylate.

5. The composition of claim 4 wherein the co-reactant is a di(meth)acrylate.

6. The composition of claim 5 wherein the co-reactant is a fluorinated di(meth)acrylate.

7. The composition of claim 1 wherein the unbranched symmetric diisocyanate is an aromatic diisocyanate.

8. The composition of claim 1 wherein the copolymer further comprises at least one chain transfer agent.

9. The composition of claim 8 wherein the chain transfer agent is selected from the group consisting of thiols, secondary alcohols, and polyhalocarbons.

10. The composition of claim 1 wherein the copolymer further comprises at least one comonomer.

11. The composition of claim 1 further comprising a solvent.

12. An article comprising a substrate having one or more surfaces coated with the composition of claim 1.

13. The article of claim 12 wherein the substrate comprises a material selected from the group consisting of polyethylene terephthalate, polyolefins, and polyolefin coated paper.

14. The article of claim 12 wherein the substrate is a fibrous substrate.

15. The article of claim 12 wherein the article is a release liner.

16. The composition of claim 11 wherein said solvent comprises water or an organic solvent.

17. The composition of claim 1 wherein the composition is a release coating composition.

18. The composition of claim 1 wherein component (c) comprises at least one hydroxy-terminated alkyl (meth)acrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

19. The composition, of claim 18 wherein the at least one hydroxy-terminated alkyl (meth)acrylate monomer comprises hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, hydroxy dodecyl acrylate, and mixtures thereof.

20. The composition of claim 1 wherein component (c) comprises at least one hydroxy-terminated 2-fluoroacrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

21. The composition of claim 5 wherein the di(meth)acrylate comprises ethylene glycol di(meth)acrylate;

diethylene glycol di(meth)acrylate;

triethylene glycol di(meth)acrylate;

tetraethylene glycol di(meth)acrylate;

1,4-butanediol di(meth)acrylate;

1,6-hexanediol di(meth)acrylate;

alkoxylated 1,6-hexanediol diacrylates;

tripropylene glycol diacrylate;

dipropylene glycol diacrylate;

cyclohexane dimethanol di(meth)acrylate;

alkoxylated cyclohexane dimethanol diacrylates;

ethoxylated bisphenol A di(meth)acrylates;

neopentyl glycol diacrylate;

polyethylene glycol di(meth)acrylates;

polypropylene glycol di(meth)acrylates;

urethane di(meth)acrylates;

C₄F₉SO₂N(CH₂CH₂OC(O)CH═

CH₂)₂;

CH₂═

CHCO₂CH₂CF₂(OCF₂CF₂)_n(OCF₂)_mCH₂OC(O)CH═

CH₂, CH₂═

CHCO₂CH₂CH₂OC(O)NH;

or C₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═

CH₂.

22. The composition of claim 5 wherein the di(meth)acrylate comprises polyethylene glycol di(meth)acrylates;

polypropylene glycol di(meth)acrylates;

1,4-butanediol di(meth)acrylate;

1,6-hexanediol di(meth)acrylate;

or CH₂═

CHCO₂CH₂CF₂(OCF₂CF₂)_n(OCF₂)_mCH₂OC(O)CH═

CH₂, CH₂═

CHCO₂CH₂CH₂OC(O)NH.

23. The composition of claim 4 wherein the co-reactant is a tri(meth)acrylate.

24. The composition of claim 23 wherein the tri(meth)acrylate comprises trimethylolpropane tri(meth)acrylate;

propoxylated trimethylolpropane triacrylates;

ethoxylated trimethylolpropane triacrylates;

tris (2-hydroxy ethyl)isocyanurate triacrylate;

or pentaerythritol triacrylate.

25. The composition of claim 10 wherein said at least one comonomer comprises methyl (meth)acrylate;

butyl acrylate;

isobutyl (meth)acrylate;

hexyl acrylate;

dodecyl acrylate;

or octadecyl acrylate.

26. A composition comprising a copolymer comprising repeating units derived from at least one co-reactant comprising two or more acrylate groups and repeating units derived from a fluoroacrylate comprising the reaction product of:

(a) at least one fluorochemical alcohol represented by the formula;

C₄F₉—

X—

OH

wherein;

27. The composition of claim 26 wherein R is a methyl group.

28. The composition of claim 26 wherein the at least one hydroxy-terminated alkyl (meth)acrylate monomer comprises hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, hydroxy dodecyl acrylate, and mixtures thereof.

29. The composition of claim 26 wherein the co-reactant comprises polyethylene glycol di(meth)acrylates;

polypropylene glycol di(meth)acrylates;

1,4-butanediol di(meth)acrylate;

1,6-hexanediol di(meth)acrylate;

or CH₂═

CHCO₂CH₂CF₂(OCF₂CF₂)_n(OCF₂)_mCH₂OC(O)CH═

CH₂, CH₂═

CHCO₂CH₂CH₂OC(O)NH.

30. The composition of claim 26 wherein the copolymer further comprises at least one comonomer.

31. The composition of claim 30 wherein said at least one comonomer comprises methyl (meth)acrylate;

butyl acrylate;

isobutyl (meth)acrylate;

hexyl acrylate;

dodecyl acrylate;

or octadecyl acrylate.

32. The composition of claim 26 wherein the composition is a release coating composition.