Low-thermal-expansion block polyimide, precursor thereof, and use thereof

Patent metadata

Field	Value
Publication number	US-9339992-B2
Application number	US-201013262253-A
Country	US
Kind code	B2
Filing date	Mar 18, 2010
Priority date	Mar 31, 2009
Publication date	May 17, 2016
Grant date	May 17, 2016

Abstract

Provided is a low-cost polyimide, containing cyclohexane diamine as a diamine unit, that has a low thermal expansion coefficient. Said block polyimide contains blocks having the repeating structural unit shown in formula (1A) and blocks having the repeating structural unit shown in formula (1B). This block polyimide is preferably obtained by imidizing a block polyamide acid imide that contains blocks having the repeating structural unit shown in formula (2A) and blocks having the repeating structural unit shown in formula (2B).

First claim

The invention claimed is:

1. A block polyimide comprising:
blocks of repeating units represented by formula (1A); and
blocks of repeating units represented by formula (1B),

where m is the number of the repeating units represented by formula (1A),
n is the number of the repeating units represented by formula (1B),
a ratio of an average value of m to an average value of n ranges from 1:9 to 9:1,
R and R″ are independently a tetravalent group having 4 to 27 carbon atoms, and independently represent an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group or a condensed polycyclic aromatic group; a non-condensed polycyclic aliphatic group in which alicyclic groups are mutually bonded to each other either directly or via a crosslinking member; or a non-condensed polycyclic aromatic group in which aromatic groups are mutually bonded to each other either directly or via a crosslinking member, and
R′ is a divalent group exclusive of 1,4-cyclohexylene having 4 to 51 carbon atoms, and represents, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, or a non-condensed polycyclic aliphatic group in which alicyclic groups are mutually bonded to each other either directly or via a crosslinking member.

2. The block polyimide according to claim 1 , wherein the ratio of the average value of m to the average value of n ranges from 2:8 to 8:2.

3. The block polyimide according to claim 1 , wherein the average value of m and the average value of n are independently 2 to 1,000.

4. The block polyimide according to claim 1 , wherein a cyclohexane skeleton in the repeating unit represented by formula (1A) has trans and cis isomers represented by formulas (1A-1) and (1A-2), respectively, and has a trans/cis ratio of 10:0 to 5:5.

5. The block polyimide according to claim 1 , wherein a logarithmic viscosity of the block polyimide in a 9:1 (weight ratio) mixture solvent of p-chlorophenol and phenol is 0.1 to 3.0 dl/g, as measured at 35° C. and at a block polyimide concentration of 0.5 g/dl.

6. A polyimide film comprising the block polyimide according to claim 1 .

7. The polyimide film according to claim 6 , wherein the number of double folds until failure in a folding endurance test is 10,000 or more and a coefficient of thermal expansion (CTE) is 10 to 30 ppm/K at 100° C. to 200° C.

8. A metal-clad laminate prepared by laminating the polyimide film according to claim 6 to a metal foil.

9. An optical film comprising the polyimide film according to claim 6 .

10. The optical film according to claim 9 , wherein the optical film is used in display device applications.

11. The optical film according to claim 9 , wherein the optical film is a transparent substrate used as a panel for display devices.

12. A display device comprising the optical film according to claim 9 .

13. A polyimide resin composition comprising:
the block polyimide according to claim 1 ; and
a coloring agent.

14. The polyimide resin composition according to claim 13 , wherein the coloring agent is a whitening agent.

15. The polyimide resin composition according to claim 14 , wherein the whitening agent is titanium oxide.

16. A light reflector comprising the polyimide resin composition according to claim 13 as a light reflecting material.

17. A display substrate material comprising the block polyimide according to claim 1 .

18. A circuit board material comprising the block polyimide according to claim 1 .

19. A coating material comprising the block polyimide according to claim 1 .

20. The block polyimide according to claim 1 , wherein R and R″ are independently a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are mutually bonded to each other either directly or via a crosslinking member.

21. A block polyamic acid/imide comprising:
blocks of repeating units represented by formula (2A); and
blocks of repeating units represented by formula (2B),

where m is the number of the repeating units represented by formula (2A),
n is the number of the repeating units represented by formula (2B),
a ratio of an average value of m to an average value of n ranges from 1:9 to 9:1,
R and R″ are independently a tetravalent group having 4 to 27 carbon atoms, and independently represent an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group or a condensed polycyclic aromatic group; a non-condensed polycyclic aliphatic group in which alicyclic groups are mutually bonded to each other either directly or via a crosslinking member; or a non-condensed polycyclic aromatic group in which aromatic groups are mutually bonded to each other either directly or via a crosslinking member, and
R′ is a divalent group exclusive of 1,4-cyclohexylene having 4 to 51 carbon atoms, and represents a monocyclic aliphatic group, a condensed polycyclic aliphatic group, or a non-condensed polycyclic aliphatic group in which alicyclic groups are mutually bonded to each other either directly or via a crosslinking member.

22. The block polyamic acid/imide according to claim 21 , wherein the ratio of the average value of m to the average value of n ranges from 2:8 to 8:2.

23. The block polyamic acid/imide according to claim 21 , wherein the average value of m and the average value of n are independently 2 to 1,000.

24. The block polyamic acid/imide according to claim 21 , wherein a polyimide composed of the repeating units represented by formula (2B) is dissolvable in aprotic polar solvents.

25. The block polyamic acid/imide according to claim 21 , wherein a logarithmic viscosity of the block polyamic acid/imide in N-methyl-2-pyrrolidone is 0.1 to 3.0 g/dl, as measured at 35° C. and at a block polyamic acid/imide concentration of 0.5 g/dl.

26. A process of producing the block polyamic acid/imide according to claim 21 , comprising:
reacting a polyamic acid composed of repeating units represented by formula (2A) with a polyimide composed of repeating units represented by formula (2B), the polyimide dissolvable in aprotic polar solvents, in an aprotic polar solvent;
wherein a cyclohexane skeleton in the repeating unit represented by formula (2A) has trans and cis isomers represented by formulas (2A-1) and (2A-2), respectively, and has a trans/cis ratio of 10:0 to 5:5.

27. A block polyamic acid/imide prepared by the process according to claim 26 .

28. A process of producing the block polyamic acid/imide according to claim 21 , comprising:
reacting an amine-terminated polyamic acid represented by formula (2A′) with an acid anhydride-terminated polyimide represented by formula (2B′) in an aprotic polar solvent;
wherein the amine-terminated polyamic acid represented by formula (2A′) is prepared from 1,4-cyclohexanediamine represented by formula (3)

Assignees

• Fukukawa Kenichi
• Urakami Tatsuhiro
• Sakata Yoshihiro
• Yamashita Wataru
• Okazaki Masaki
• Mitsui Chemicals Inc

Inventors

• Fukukawa Kenichi
• Urakami Tatsuhiro
• Sakata Yoshihiro
• Yamashita Wataru
• Okazaki Masaki

Classifications

• B32B15/08 Primary

  of synthetic resin · CPC title

• H05K1/0346

  containing N · CPC title

• C08G73/10 Primary

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• B32B27/281

  comprising polyimides · CPC title

• Y10T428/31681

  Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.] · CPC title