Modified copolyesters and improved multilayer reflective films

• US 6,352,761 B1
• Filed: 01/15/1999
• Issued: 03/05/2002
• Est. Priority Date: 01/13/1998
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Hebrink, Timothy J., Stover, Carl A., Merrill, William W.
• Primary Examiner(s): Chen, Vivian
• Application Number:
  US09/232,332
• Time in Patent Office: 1,145 Days
• Field of Search: 428/910, 428/480, 428/483, 428/212, 359/580, 359/586, 359/587, 359/577, 359/589, 359/485, 359/487, 359/494, 359/500, 528/302, 528/305, 528/307, 528/308, 528/308.6
• US Class Current: 428/212
• CPC Class Codes: A61B 5/0803 Recording apparatus specially adapted therefor
• CPC Class Codes: A61B 5/0809 by impedance pneumography
• CPC Class Codes: A61B 5/0816 Measuring devices for examining respiratory frequency measuring frequency of electric signals G01R23/00
• CPC Class Codes: A61B 5/22 Ergometry; Measuring muscular strength or the force of a muscular blow exercising apparatus A63B21/00 ; measuring of work or force in general G01L
• CPC Class Codes: A61N 1/3627 for treating a mechanical deficiency of the heart, e.g. congestive heart failure or cardiomyopathy
• CPC Class Codes: A61N 1/36514 controlled by a physiological quantity other than heart potential, e.g. blood pressure controlled by two or more physical parameters A61N1/36585
• CPC Class Codes: A61N 1/3704 Circuits specially adapted therefor, e.g. for sensitivity control
• CPC Class Codes: B32B 2250/05 5 or more layers
• CPC Class Codes: B32B 2250/244 All polymers belonging to those covered by group B32B27/36
• CPC Class Codes: B32B 2255/10 on synthetic resin layer or on natural or synthetic rubber layer
• CPC Class Codes: B32B 2255/20 Inorganic coating
• CPC Class Codes: B32B 2255/26 Polymeric coating
• CPC Class Codes: B32B 2307/416 Reflective
• CPC Class Codes: B32B 2307/42 Polarizing, birefringent, filtering
• CPC Class Codes: B32B 2307/5825 Tear resistant
• CPC Class Codes: B32B 2307/584 Scratch resistance
• CPC Class Codes: B32B 2307/704 Crystalline
• CPC Class Codes: B32B 2457/202 LCD, i.e. liquid crystal displays
• CPC Class Codes: B32B 2551/00 Optical elements
• CPC Class Codes: B32B 2551/08 Mirrors
• CPC Class Codes: B32B 27/08 : of synthetic resin
• CPC Class Codes: B32B 27/36 : comprising polyesters
• CPC Class Codes: B32B 7/023 : Optical properties
• CPC Class Codes: C08G 63/181 : Acids containing aromatic rings
• CPC Class Codes: C08G 63/199 : Acids or hydroxy compounds containing cycloaliphatic rings
• CPC Class Codes: C08G 63/20 : Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• CPC Class Codes: G02B 5/0841 : comprising organic materials, e.g. polymers
• CPC Class Codes: G02B 5/0866 : incorporating one or more organic, e.g. polymeric layers
• CPC Class Codes: G02B 5/305 : including organic materials, e.g. polymeric layers
• CPC Class Codes: G02B 5/3083 : Birefringent or phase retarding elements G02B5/3008, G02B5/3016 take precedence; systems for polarisation control G02B27/286; manufacturing phase modulating patterns by lithographic processes G03F7/001
• CPC Class Codes: Y10S 428/91 : Product with molecular orientation
• CPC Class Codes: Y10T 428/11 : Magnetic recording head
• CPC Class Codes: Y10T 428/24479 : including variation in thickness
• CPC Class Codes: Y10T 428/24612 : Composite web or sheet
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31786 : Of polyester [e.g., alkyd, etc.]

Abstract

A multilayered polymer film includes a first set of optical layers and a second set of optical layers. The first set of optical layers is made from a polyester which is often birefringent. The polyesters of the first set of optical layers typically have a composition in which 70-100 mol % of the carboxylate subunits are first carboxylate subunits and 0-30 mol % are comonomer carboxylate subunits and 70 to 100 mol % of the glycol subunits are first glycol subunits and 0 to 30 mol % of the glycol subunits are comonomer glycol subunits, where at least 0.5 mol % of the combined carboxylate and glycol subunits are comonomer carboxylate or comonomer glycol subunits. The second set of optical layers comprise copolyesters wherein 0.01 to 2.5 mol % of the combined carboxylate and glycol subunits are carboxylate subunits derived from compounds having three or more carboxylate or ester functionalities, glycol subunits derived from compounds having three or more hydroxyl functionalities, or combinations thereof. The multilayered polymer film may be used to form, for example, a reflective polarizer or a mirror.

Claims

1. A multilayered polymer film, comprising:

a plurality of first optical layers comprising a first copolyester, the first copolyester being semicrystalline and birefringent, the first copolyester comprising carboxylate subunits and glycol subunits, wherein 70 to 100 mol % of the carboxylate subunits are first carboxylate subunits, 0 to 30 mol % of the carboxylate subunits are first comonomer carboxylate subunits, 70 to 100 mol % of the glycol subunits are first glycol subunits, and 0 to 30 mol % of the glycol subunits are first comonomer glycol subunits, and wherein at least 2.5 mol % of the combined carboxylate and glycol subunits of the first copolyester are first comonomer carboxylate subunits, first comonomer glycol subunits, or a combination thereof; and

a plurality of second optical layers comprising a second copolyester having an in-plane birefringence of about 0.04 or less, at 632.8 nm, after the multilayered polymer film has been formed, the second copolyester comprising carboxylate subunits and glycol subunits, the carboxylate subunits comprising 20 to 100 mol % second carboxylate subunits and 0 to 80 mol % second comonomer carboxylate subunits, the glycol subunits comprising 40 to 100 mol % second glycol subunits and 0 to 60 mol % second comonomer glycol subunits, wherein 10 mol % or more of the combined carboxylate and glycol subunits of the second copolyester are second comonomer carboxylate subunits, second comonomer glycol subunits, or a combination thereof,

wherein 0.01 to 2.5 mol % of the combined carboxylate and glycol subunits of the second copolyester are second comonomer carboxylate subunits derived from compounds having three or more carboxylate or ester functionalities, second comonomer glycol subunits derived from compounds having three or more hydroxy functionalities, or a combination thereof.

2. The multilayered polymer film of claim 1, wherein one in-plane index of refraction of the first copolyester is approximately equal to one in-plane index of refraction of the second copolyester after the multilayered polymer film has been formed.

3. The multilayered polymer film of claim 1, wherein the two indices of refraction that are approximately equal differ by about 0.05 or less.

4. The multilayered polymer film of claim 1, wherein the two indices of refraction that are approximately equal differ by about 0.02 or less.

5. The multilayered polymer film of claim 1, wherein the first and second carboxylate subunits are the same.

6. The multilayered polymer film of claim 1, wherein, after the multilayered polymer film is formed, the first copolyester has an in-plane birefringence of 0.1 or greater at 632.8 nm.

7. The multilayered polymer film of claim 1, wherein the first comonomer carboxylate subunits are naphthalate, terephthalate or isophthalate subunits or a combination thereof.

8. The multilayered polymer film of claim 1, wherein the first glycol subunits are generated from C2-C8 diols.

9. The multilayered polymer film of claim 8, wherein the first glycol subunits are derived from ethylene glycol, propylene glycol, or 1,4-butanediol.

10. The multilayered polymer film of claim 1, wherein the first copolyester is birefringent after being stretched in a stretch direction.

11. The multilayered polymer film of claim 1, wherein the multilayered polymer film further comprises one or more non-optical layers.

12. The multilayered polymer film of claim 11, wherein the plurality of first and second layers form a stack of layers and one or more of the non-optical layers are formed over the stack of layers.

13. The multilayered polymer film of claim 11, wherein the plurality of first and second layers form a stack of layers and one or more of the non-optical layers are disposed within the stack of layers.

14. The multilayered polymer film of claim 1, wherein the second copolyester comprises glycol subunits derived from 85 to 99.99 mol % C2-C4 diols and 0.01 to 5 mol % compounds having three or more hydroxy functionalities and carboxylate subunits derived only from 5 to 95 mol % cyclohexane dicarboxylic acid or lower alkyl esters thereof and 5 to 95 mol % tertiary-butyl isophthalic acid or lower alkyl esters thereof.

15. The multilayered polymer film of claim 1, wherein the multilayered polymer film is a multilayered optical film that at least partially reflects light having a first polarization direction and substantially transmits light having a second polarization directions that is orthogonal to the first polarization direction.

16. The multilayered optical film of claim 1, wherein at least two in-plane indices of refraction of the first copolyester are greater than the corresponding in-plane indices of refraction of the second copolyester after the multilayered polymer film has been formed.

17. The multilayered polymer film of claim 16, wherein the first glycol subunits are generated from C2-C8 diols.

18. The multilayered polymer film of claim 16, wherein the first glycol subunits are derived from ethylene glycol, propylene glycol, or 1,4-butanediol.

19. A multilayered optical film, comprising:

a plurality of first optical layers comprising a first copolyester, the first copolyester being semicrystalline and birefringent; and

a plurality of second optical layers comprising a second copolyester having an in-plane birefringence of about 0.04 or less, at 632.8 nm, after the multilayered optical film has been formed, the second copolyester comprising carboxylate subunits and glycol subunits, wherein 0.01 to 2.5 mol % of the combined carboxylate and glycol subunits are derived from compounds with three or more carboxylate or ester functional groups, compounds with three or more hydroxy functional groups, or a combination thereof.

20. The multilayered optical film of claim 19, wherein one in-plane index of refraction of the first copolyester is approximately equal to one in-plane index of refraction of the second copolyester after the multilayered optical film has been formed.

21. The multilayered optical film of claim 20, wherein the two indices of refraction that are substantially equal differ by about 0.05 or less.

22. The multilayered optical film of claim 20, wherein the two indices of refraction that are substantially equal differ by about 0.02 or less.

23. The multilayered optical film of claim 19, wherein at least two in-plane indices of refraction of the first copolyester are greater than the corresponding in-plane indices of refraction of the second copolyester after the multilayered polymer film has been formed.

24. A multilayered polymer film, comprising:

a plurality of first optical layers comprising a first copolyester, the first copolyester being semicrystalline and birefringent, the first copolyester comprising carboxylate subunits and glycol subunits, wherein 70 to 100 mol % of the carboxylate subunits are first carboxylate subunits, 0 to 30 mol % of the carboxylate subunits are first comonomer carboxylate subunits, 70 to 100 mol % of the glycol subunits are first glycol subunits, and 0 to 30 mol % of the glycol subunits are first comonomer glycol subunits, and wherein at least 2.5 mol % of the combined carboxylate and glycol subunits of the first copolyester are first comonomer carboxylate subunits, first comonomer glycol subunits, or a combination thereof; and

a plurality of second optical layers comprising a second polymer having an in-plane birefringence of about 0.04 or less, at 632.8 nm, after the multilayered polymer film has been formed,

wherein the second polymer of the second optical layers comprises a second copolyester having an intrinsic viscosity of about 0.4 dL/g or greater and comprising glycol subunits and carboxylate subunits,

the glycol subunits derived from 70 to 99 mol % C2-C4 diols and about 1 to 30 mol % comonomer glycol subunits derived from 1,6-hexanediol, and

the carboxylate subunits being 5 to 99 mol % naphthalate subunits, 1 to 95 mol % terephthalate or isophthalate subunits or mixtures thereof, and 0 to 30 mol % of comonomer carboxylate subunits derived from phthalic acid, t-butyl-isophthalic acid, lower alkyl esters of these acids, or a combination thereof;

wherein at least 0.01 to 2.5 mol % of the combined carboxylate and glycol subunits of the second copolyester are derived from compounds having three or more carboxylate, ester, or hydroxy functional groups.

25. The multilayered optical film of claim 24, wherein one in-plane index of refraction of the first copolyester is approximately equal to one in-plane index of refraction of the second polymer after the multilayered polymer film has been formed.

26. The multilayered polymer film of claim 25, wherein the two indices of refraction that are approximately equal differ by about 0.05 or less.

27. The multilayered polymer film of claim 25, wherein the two indices of refraction that are approximately equal differ by about 0.02 or less.

28. The multilayered polymer film of claim 24, wherein the first glycol subunits are generated from C2-C8 diols.

29. The multilayered polymer film of claim 24, wherein the first glycol subunits are derived from ethylene glycol, propylene glycol, or 1,4-butanediol.

30. The multilayered polymer film of claim 24, wherein at least two in-plane indices of refraction of the first copolyester are greater than the corresponding in-plane indices of refraction of the second polymer after the multilayered polymer film has been formed.

31. The multilayered polymer film of claim 30, wherein the first glycol subunits are generated from C2-C8 diols.

32. The multilayered polymer film of claim 30, wherein the first glycol subunits are derived from ethylene glycol, propylene glycol, or 1,4-butanediol.

33. A multilayered polymer film, comprising:

a plurality of birefringent first layers comprising a first copolyester having naphthalate subunits;

a plurality of second layers comprising a second copolyester, the second copolyester having an intrinsic viscosity of 0.4-0.5 dL/g, the second copolyester comprising between about 0.01 to 5 mol % comonomer subunits which are derived from compounds having three or more carboxylate, ester, or hydroxy functional groups; and

one or more non-optical layers, the non-optical layers having an intrinsic viscosity of 0.5 dL/g or greater.

34. The multilayered optical film of claim 33, wherein one in-plane index of refraction of the first copolyester is approximately equal to one in-plane index of refraction of the second polymer after the multilayered polymer film has been formed.

35. The multilayered polymer film of claim 34, wherein the second copolyester comprises carboxylate subunits and glycol subunits, the carboxylate subunits comprising 20 to 100 mol% second carboxylate subunits and 0 to 80 mol% second comonomer carboxylate subunits, the glycol subunits comprising 40 to 100 mol% second glycol subunits and 0 to 60 mol% second comonomer glycol subunits, wherein 10 mol% or more of the combined carboxylate and glycol subunits of the second polymer are second comonomer carboxylate subunits, second comonomer glycol subunits, or a combination thereof.

36. The multilayered polymer film of claim 34, wherein the two indices of refraction that are approximately equal differ by about 0.05 or less.

37. The multilayered polymer film of claim 34, wherein the two indices of refraction that are approximately equal differ by about 0.02 or less.

38. The multilayered polymer film of claim 33, wherein at least two in-plane indices of refraction of the first copolyester are greater than the corresponding in-plane indices of refraction of the second copolyester after the multilayered polymer film has been formed.

39. The multilayered polymer film of claim 38, wherein the second copolyester comprises carboxylate subunits and glycol subunits, the carboxylate subunits comprising 20 to 100 mol % second carboxylate subunits and 0 to 80 mol % second comonomer carboxylate subunits, the glycol subunits comprising 40 to 100 mol % second glycol subunits and 0 to 60 mol % second comonomer glycol subunits, wherein 10 mol % or more of the combined carboxylate and glycol subunits of the second polymer are second comonomer carboxylate subunits, second comonomer glycol subunits, or a combination thereof.

40. A multilayered polymer film, comprising:

a plurality of first optical layers comprising a first copolyester, the first copolyester being semicrystalline and birefringent, the first copolyester comprising carboxylate subunits and glycol subunits, wherein 70 to 100 mol % of the carboxylate subunits are first carboxylate subunits, the first carboxylate subunits being naphthalate or terephthalate subunits, 0 to 30 mol % of the carboxylate subunits are first comonomer carboxylate subunits, 70 to 100 mol % of the glycol subunits are first glycol subunits, and 0 to 30 mol % of the glycol subunits are first comonomer glycol subunits, and wherein at least 2.5 mol % of the combined carboxylate and glycol subunits of the first copolyester are first comonomer carboxylate subunits, first comonomer glycol subunits, or a combination thereof; and

a plurality of second optical layers comprising a second copolyester having an in-plane birefringence of about 0.04 or less, at 632.8 nm, after the multilayered polymer film has been formed, wherein the second copolyester comprises glycol subunits derived from 85 to 99.99 mol % C2-C4 diols and 0.01 to 5 mol % branching monomer molecules and carboxylate subunits derived only from 5 to 95 mol % cyclohexane dicarboxylic acid or lower alkyl esters thereof and 5 to 95 mol % tertiary-butyl isophthalic acid or lower alkyl esters thereof;

wherein at least two in-plane indices of refraction of the first copolyester are greater than the corresponding in-plane indices of refraction of the second polymer after the multilayered polymer film has been formed.

41. The multilayered polymer film of claim 40, wherein, after the multilayered polymer film is formed, the first copolyester has an in-plane birefringence of 0.1 or greater at 632.8 nm.

42. The multilayered polymer film of claim 40, wherein the first comonomer carboxylate subunits are naphthalate, terephthalate or isophthalate subunits or a combination thereof.

43. The multilayered polymer film of claim 40, wherein the first glycol subunits are generated from C2-C8 diols.

44. The multilayered polymer film of claim 43, wherein the first glycol subunits are derived from ethylene glycol, propylene glycol, or 1,4-butanediol.

45. The multilayered polymer film of claim 40, wherein the first copolyester is birefringent after being stretched in a stretch direction.

46. The multilayered polymer film of claim 40, wherein the multilayered polymer film further comprises one or more non-optical layers.

47. The multilayered polymer film of claim 46, wherein the plurality of first and second layers form a stack of layers and one or more of the non-optical layers are formed over the stack of layers.

48. The multilayered polymer film of claim 46, wherein the plurality of first and second layers form a stack of layers and one or more of the non-optical layers are disposed within the stack of layers.

49. A polymer comprising:

a copolyester comprising glycol subunits and carboxylate subunits;

wherein the glycol subunits are derived from 85 to 99.99 mol % C2-C4 diols and 0.01 to 5 mol % branching monomer molecules; and

the carboxylate subunits are all derived from 5 to 95 mol % cyclohexane dicarboxylic acid or lower alkyl esters thereof and 5 to 95 mol % tertiary-butyl isophthalic acid or lower alkyl esters thereof.