KR20070032246A - Polycyclic polyimides and compositions and methods relating thereto - Google Patents

Abstract

The present invention relates to useful polycyclic diamines. Such diamines are used to form new polyamic acids when polymerized with dianhydrides and optionally other non-polycyclic diamines. Polyamic acids can be imidized to form new classes of useful polyimide resins and polyimide films, in particular polyimide resins and polyimide films of the electronics category.

Polycyclic diamines, polyamic acids, polyimides, dianhydrides, translucent

Description

POLYCYCLIC POLYIMIDES AND COMPOSITIONS AND METHODS RELATING THERETO

1. Technology Field

The present invention relates generally to polycyclic polyimides, including methods and compositions related to polycyclic polyimides. More specifically, the compositions and methods of the present invention are derived from cycloaliphatic diamine isomers, in particular to provide polycyclic polyimides having advantageous properties as glass substitutes for certain electronic products.

2. Background

There is a need for commercially viable glass or quartz substitutes for applications in display screens or other similar types of optical communications. Conventional polyimides are generally not well suited for this use.

US Pat. No. 6,710,160, US Pat. No. 6,734,276 and US Pat. No. 6,812,065 (Mitsui Chemicals Inc.) disclose diamine mixtures of 2,5-NBDA and 2,6-NBDA. . However, such diamines are not well suited for providing polyimides having sufficient glass transition temperature, light transmittance, and coefficient of thermal expansion ("CTE") as suitable substitutes for quartz or glass in optical display devices and the like.

Summary of the Invention

Polyimide of the present invention may be represented by the formula (1).

<Formula 1>

In the formula,

R is -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -CH ₃ ,-(CH ₂ ) ₄ -CH ₃ , -CX ₃ , -CH ₂ -CX ₃ , -CH ₂ -CH ₂ -CX ₃ ,-(CH ₂ ) ₃ -CX ₃ ,-(CH ₂ ) ₄ -CX ₃ , where X is F, Cl or Br, -C ₆ H ₅ (a 6-membered aromatic ring) and C ₆ H ₅ -CH ₃ , wherein the methyl group is in the ortho or para position in the 6-membered aromatic ring,

R ₁ is a tetravalent group having 4 to 27 carbon atoms and is an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group, a polycyclic aromatic group, a substituted aliphatic or aromatic group (e.g., fluorine ), From the group comprising non-condensed polycyclic aliphatic groups or aromatic groups (or mixtures thereof) condensed aromatic groups, and / or cyclic aliphatic groups or aromatic groups connected to one another directly or via bridging groups. Selected,

k is any integer of 0, 1, and 2,

n is an integer in the range between and including any two numbers of 10, 100, 1000, 10,000, and 100,000.

The present invention also includes polyamic acid precursors of the polyimide and also includes a method of converting such polyamic acid to such polyimide. The polycyclic polyimide of the present invention may be embodied as a polyimide resin, polyimide varnish or coating, and / or polyimide film.

The polyimide (or polyamic acid precursor thereof) may be derived from the reaction product of the diamine component and the dianhydride component, which may comprise (at least partially) a diamine monomer represented by the following formula (2).

<Formula 2>

In the formula,

R is -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -CH ₃ ,-(CH ₂ ) ₄ -CH ₃ , -CX ₃ , -CH ₂ -CX ₃ , -CH ₂ -CH ₂ -CX ₃ ,-(CH ₂ ) ₃ -CX ₃ ,-(CH ₂ ) ₄ -CX ₃ , where X is F, Cl or Br, -C ₆ H ₅ (six-membered aromatic ring) and C ₆ H ₅ -CH ₃ , wherein the methyl group is in the ortho or para position in the six-membered aromatic ring,

k is an integer and may be 0, 1 or 2.

In one embodiment, the diamine component comprises (at least partially) a diamine monomer represented by the following formula (3).

<Formula 3>

However, in such diamines, the —CH ₃ group (ie, a single accessory methyl group) is linked to at least one of the carbon atoms bonded to at least one of the depicted —CH ₂ NH ₂ groups. In such diamines, k is an integer and can be 0, 1 or 2.

The diamines of formula (2) are present alone in the polyimide of the present invention (ie, the only diamine in the total diamine component) or together with other diamines, provided that the diamine is present in large quantities sufficient to exhibit advantageous properties. In addition, the diamines may appear to have a variety of different isomers and structural ligands (and typically those having a variety of different isomers and structural ligands are used). For example, the diamine of formula (2) may have an orientation in which the —CH ₂ NH ₂ groups and the R groups of the norbornane skeleton may vary in position. However, in such diamines, the R group is linked to at least one of the carbon atoms bonded to at least one of the -CH ₂ NH ₂ groups shown.

In one embodiment of the invention, the diamine (-CH _2- ) crosslinking (i.e. when k is 1 or 2) of k repeat units is on the same side or opposite to the other crosslinking group (s) -CH _2- Can be in.

In another embodiment of the invention, the polycyclic polyimide is prepared by a method comprising combining the diamine of formula (2) with tetracarboxylic dianhydride. It is contemplated that the reaction product of the diamine and one or more dianhydrides is at least partially or partially represented by the following formula (4).

<Formula 4>

In the formula,

R ₁ is an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group, a polycyclic aromatic group, a substituted aliphatic or aromatic group (eg fluorine), a condensed aromatic group and / or A C ₄ to C ₂₇ carbon structure selected from the group comprising a non-condensed polycyclic aliphatic group or an aromatic group (or a mixture thereof) linked to each other by a click aliphatic group or an aromatic group directly or via a crosslinking group,

n is an integer between any two numbers of 10, 100, 1000, 10,000 and 100,000.

In the polyimides (and polyamic precursors) of the present invention, the diamines of formula (3) may generally exist in at least eight different isomeric structures (where k is zero, as well as k is 1 or 2 Listed). Such isomeric structures may be represented by at least the following formula.

In another embodiment, a polycyclic polyimide of the present invention comprises a step of combining a diamine of formula (2) with at least one tetracarboxylic dianhydride, and optionally another diamine represented by formula (5) Is formed by.

<Formula 5>

NH ₂ -X-NH ₂

In the formula,

X may represent a divalent alicyclic group, a divalent aliphatic group (except the divalent group described in Formula 2), a divalent aromatic group, a substituted aliphatic or aromatic group (eg, fluorine) or a divalent siloxane containing group.

In one embodiment, the present invention relates to a polyimide and polyamic acid solution, derived from a diamine represented by the following formula (2).

<Formula 2>

In the formula,

R is -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -CH ₃ ,-(CH ₂ ) ₄ -CH ₃ , -CX ₃ , -CH ₂ -CX ₃ , -CH ₂ -CH ₂ -CX ₃ ,-(CH ₂ ) ₃ -CX ₃ ,-(CH ₂ ) ₄ -CX ₃ , where X is F, Cl or Br, -C ₆ H ₅ (a 6-membered aromatic ring) and C ₆ H ₅ -CH ₃ , wherein the methyl group is in the ortho or para position in the 6-membered aromatic ring,

k is an integer and may be 0, 1 or 2.

Diamines useful according to the present invention include diamine monomers represented by the following formula (3).

<Formula 3>

In such diamines, the —CH ₃ group (ie, a single accessory methyl group) is linked to at least one of the carbon atoms bonded to at least one of the depicted —CH ₂ NH ₂ groups. In such diamines, k is an integer and can be 0, 1 or 2.

The diamine of Formula 2 may be polymerized with a dianhydride component to form a polyamic acid, and may be thermoset through a polycondensation reaction to form a polyimide represented by the following Formula 4.

<Formula 4>

In the formula,

R ₁ is an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group, a polycyclic aromatic group, a substituted aliphatic or aromatic group (eg fluorine substituted), a condensed aromatic group, and And / or a C ₄ to C ₂₇ carbon structure selected from the group comprising non-condensed polycyclic aliphatic groups or aromatic groups (or mixtures thereof) linked to each other directly or via a crosslinking group,

n is an integer between any two numbers (including any two numbers) of 10, 100, 1000, 10,000, and 100,000.

One example of the diamine of formula (2) may also be represented by formula (more specifically) below.

<Formula 6>

In Formula 6, diamine (IUPAC nomenclature) may be referred to as [5- (aminomethyl) -5-methylbicyclo [2.2.1] heptan-2-yl] methylamine.

Another example of the diamine of formula (2) may also be represented by formula (7).

<Formula 7>

In Chemical Formula 7, diamine (IUPAC nomenclature) may be referred to as [6- (aminomethyl) -6-methylbicyclo [2.2.1] heptan-2-yl] methylamine.

In some instances, when one example of the diamine of Formula 2 is synthesized or prepared, the diamine product prepared by the above synthesis method (or the above preparation method) may be [5- (aminomethyl) -5-methylbicyclo [2.2.1]. Heptane-2-yl] methylamine and [6- (aminomethyl) -6-methylbicyclo [2.2.1] heptan-2-yl] methylamine. Thus, the above combination of diamines (represented as a combination of diamines represented by Formula 6 and Formula 7) is 2,5- (or 6) -bis (aminomethyl) -2-methyl-bicyclo [2.2 for the purposes of the present invention. .1] heptane.

In the polyimides (and polyamic precursors) of the present invention, the diamines of formula (3) may exist in at least eight different isomeric structures (as described herein when k is 0, as well as when k is 1 or 2). ). Such isomeric structures can be represented by the following formula.

In one embodiment of the present invention, the polyimide is formed using a diamine of formula (2) with at least one other diamine and tetracarboxylic dianhydride represented by formula (5) below.

<Formula 5>

NH ₂ -X-NH ₂

In the formula,

X may represent a divalent alicyclic group, a divalent aliphatic group (except the divalent group described in Formula 2), a divalent aromatic group, a substituted aliphatic or aromatic group (eg, fluorine) or a divalent siloxane containing group.

Substituted diamines are 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, It may be present in the diamine component in an amount between any two numbers of 95 and 99 mol% and in the range including them. In one embodiment of the invention, the diamines of formula (2) are used in amounts ranging from 3 to 50 mole percent of the total diamine component.

Useful diamines include, but are not limited to:

1. trans-1,4-diaminocyclohexane;

2. diaminocyclooctane;

3. tetramethylenediamine;

4. hexamethylenediamine;

5. octamethylenediamine;

6. nonamethylenediamine;

7. decamethylenediamine;

8. dodecamethylenediamine;

9. aminomethylcyclooctylmethanamine;

10. aminomethylcyclododecylmethanamine;

11. aminomethylcyclohexylmethanamine;

12. 4,4'-diaminodiphenyl methane;

13. 4,4'-diaminodiphenyl sulfide (4,4'-DDS);

14. 3,3'-diaminodiphenyl sulfone (3,3'-DDS);

15. 4,4'-diaminodiphenyl sulfone;

16. 4,4'-diaminodiphenyl ether (4,4'-ODA);

17. 3,4'-diaminodiphenyl ether (3,4'-ODA);

18. 1,3-bis- (4-aminophenoxy) benzene (APB-134);

19. 1,3-bis- (3-aminophenoxy) benzene (APB-133);

20. 1,2-bis- (4-aminophenoxy) benzene;

21. 1,2-bis- (3-aminophenoxy) benzene;

22. 1,4-bis- (4-aminophenoxy) benzene (APB-144);

23. 1,4-bis- (3-aminophenoxy) benzene;

24. 1,5-diaminonaphthalene;

25. 1,8-diaminonaphthalene;

26. 2,2'-bis (trifluoromethyl) benzidine (TFMB);

27. 4,4'-diaminodiphenyldiethylsilane;

28. 4,4'-diaminodiphenylsilane;

29. 4,4'-diaminodiphenyl-N-methyl amine;

30. 4,4'-diaminodiphenyl-N-phenyl amine;

31. 1,2-diaminobenzene (OPD);

32. 1,3-diaminobenzene (MPD);

33. 1,4-diaminobenzene (PPD);

34. 2,5-dimethyl-1,4-diaminobenzene;

35. 2- (trifluoromethyl) -1,4-phenylenediamine;

36. 5- (trifluoromethyl) -1,3-phenylenediamine;

37. 2,2-bis [4- (4-aminophenoxy) phenyl] -hexafluoropropane;

38. 2,2-bis (3-aminophenyl) 1,1,1,3,3,3-hexafluoropropane;

39. benzidine;

40. 4,4'-diaminobenzophenone;

41. 3,4'-diaminobenzophenone;

42. 3,3'-diaminobenzophenone;

43. m-xylylene diamine;

44. bisaminophenoxyphenylsulfone;

45. 4,4'-isopropylidenedianiline;

46. N, N-bis- (4-aminophenyl) methylamine;

47. N, N-bis- (4-aminophenyl) aniline;

48. 3,3'-dimethyl-4,4'-diaminobiphenyl;

49. 4-aminophenyl-3-aminobenzoate;

50. 2,4-diaminotoluene;

51. 2,5-diaminotoluene;

52. 2,6-diaminotoluene;

53. 2,4-diamine-5-chlorotoluene;

54. 2,4-diamine-6-chlorotoluene;

55. 4-chloro-1,2-phenylenediamine;

56. 4-chloro-1,3-phenylenediamine;

57. 2,4-bis- (beta-amino-t-butyl) toluene;

58. bis- (p-beta-amino-t-butyl phenyl) ether;

59. p-bis-2- (2-methyl-4-aminopentyl) benzene;

60. 1- (4-aminophenoxy) -3- (3-aminophenoxy) benzene;

61. 1- (4-aminophenoxy) -4- (3-aminophenoxy) benzene;

62. 2,2-bis- [4- (4-aminophenoxy) phenyl] propane (BAPP);

63. bis- [4- (4-aminophenoxy) phenyl] sulfone (BAPS);

64. 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone (m-BAPS);

65. 4,4'-bis- (aminophenoxy) biphenyl (BAPB);

66. bis (4- [4-aminophenoxy] phenyl) ether (BAPE);

67. 2,2'-bis- (4-aminophenyl) -hexafluoropropane (6F diamine);

68. 2,2'-bis- (4-phenoxyaniline) isopropylidene;

69. 2,4,6-trimethyl-1,3-diaminobenzene;

70. 4,4'-diamino-2,2'-trifluoromethyl diphenyloxide;

71. 3,3'-diamino-5,5'-trifluoromethyl diphenyloxide;

72. 4,4'-trifluoromethyl-2,2'-diaminobiphenyl;

73. 4,4'-oxy-bis-[(2-trifluoromethyl) benzene amine];

74. 4,4'-oxy-bis-[(3-trifluoromethyl) benzene amine];

75. 4,4'-thio-bis-[(2-trifluoromethyl) benzene amine];

76. 4,4'-thiobis-[(3-trifluoromethyl) benzene amine];

77. 4,4'-Sulfoxyl-bis-[(2-trifluoromethyl) benzene amine];

78. 4,4'-Sulfoxy-bis-[(3-trifluoromethyl) benzene amine];

79. 4,4'-keto-bis-[(2-trifluoromethyl) benzene amine];

80. 9,9-bis (4-aminophenyl) fluorene;

81. 1,3-diamino-2,4,5,6-tetrafluorobenzene;

82. 3,3'-bis (trifluoromethyl) benzidine;

83. 4,4'-diaminobenzanilide,

84. o-tolidine sulfone;

85. o-tolidine disulfonic acid;

86. 4,4'-diamino-3,3'-dicarboxy-diphenyl methane;

87. 9,9-bis (4-aminophenyl) fluorene;

88. 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane;

89. diaminodurene;

90. 3,3 ', 5,5'-tetramethylbenzidine;

91. a, w-bis (4-aminophenoxy) alkanes;

92. 1,3-diamino-2,4,5,6-tetrafluorobenzene;

93. Miscellaneous.

Other possible diamines include divalent aromatic diamines (eg, diaminosiloxanes) including divalent alicyclic diamines, divalent aliphatic / aromatic diamines, and siloxane groups. Polysiloxane diamine, as used herein, is intended to mean a diamine having one or more polysiloxane residues (eg, shown in parentheses in the formula below). For example, useful polysiloxane diamines may have the following formula (8).

<Formula 8>

NH ₂ -R ₁ -O- [SiR'R "-O-] _m -R ₁ -NH ₂

In the formula,

R 'and R "are-(CH ₃ ) or-(C ₆ H ₅ ),

R _1- (CH ₂ ) -n,

n is about 1 to 10 (preferably about 3),

m is 1 to 40, but may be 1 to 12 or 8 to 10.

Typical diaminosiloxanes are 3,3 '-(1,1,3,3,5,5-hexamethyl-1,5-trisiloxanediyl) -bis-1-propanamine.

Tetracarboxylic dianhydride can be used to prepare the polyimide (and polyamic acid precursor) of the present invention. Such dianhydrides can generally be selected from a variety of materials including alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and / or aromatic tetracarboxylic dianhydrides. Such dianhydrides can also be used in the form of derivatives such as diacid-diesters, diacid halide esters, and tetracarboxylic acids. In one example, the use of aliphatic tetracarboxylic dianhydrides generally leads to the formation of polyimides having good optical properties, including transparency, even though often abandon thermal stability. Aromatic tetracarboxylic dianhydrides typically produce polyimides having good thermal properties such as heat resistance and thermal stability. In general, the diamines of the present invention, used in combination with conventional aromatic tetracarboxylic dianhydrides, allow for the production of polyimides that exhibit improved thermal stability along with improved optical clarity making the polyimide useful for electronic device applications. can do.

Examples of useful dianhydrides of the present invention include the following.

1. pyromellitic dianhydride (PMDA);

2. 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA);

3. 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA);

4. 4,4'-oxydiphthalic anhydride (ODPA);

5. 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA);

6. 4,4 '-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride) (BPADA);

7. 2,3,6,7-naphthalene tetracarboxylic dianhydride;

8. 1,2,5,6-naphthalene tetracarboxylic dianhydride;

9. 1,4,5,8-naphthalene tetracarboxylic dianhydride;

10. 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride;

11. 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride;

12. 2,3,3 ', 4'-biphenyl tetracarboxylic dianhydride;

13. 2,2 ', 3,3'-biphenyl tetracarboxylic dianhydride;

14. 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride;

15. 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride;

16. 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride;

17. 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride;

18. 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride;

19. bis (2,3-dicarboxyphenyl) methane dianhydride;

20. bis (3,4-dicarboxyphenyl) methane dianhydride;

21. 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA);

22. bis (3,4-dicarboxyphenyl) sulfoxide dianhydride;

23. tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride;

24. pyrazine-2,3,5,6-tetracarboxylic dianhydride;

25. Thiophene-2,3,4,5-tetracarboxylic dianhydride;

26. phenanthrene-1,8,9,10-tetracarboxylic dianhydride;

27. Perylene-3,4,9,10-tetracarboxylic dianhydride;

28. bis-1,3-isobenzofurandione;

29. bis (3,4-dicarboxyphenyl) thioether dianhydride;

30. Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;

31. 2- (3 ', 4'-dicarboxyphenyl) -5,6-dicarboxybenzimidazole dianhydride;

32. 2- (3 ', 4'-dicarboxyphenyl) -5,6-dicarboxybenzoxazole dianhydride;

33. 2- (3 ', 4'-dicarboxyphenyl) -5,6-dicarboxybenzothiazole dianhydride;

34. bis (3,4-dicarboxyphenyl) -2,5-oxadiazole-1,3,4-dianhydride;

35. bis 2,5- (3 ', 4'-dicarboxydiphenylether) -1,3,4-oxadiazole dianhydride;

36. butane-1,2,3,4-tetracarboxylic dianhydride;

37. pentane-1,2,4,5-tetracarboxylic dianhydride;

38. cyclobutane tetracarboxylic dianhydride;

39. cyclopentane-1,2,3,4-tetracarboxylic dianhydride;

40. cyclohexane-1,2,4,5-tetracarboxylic dianhydride;

41. cyclohexane-2,3,5,6-tetracarboxylic dianhydride;

42. 3-ethyl cyclohexane-3- (1,2) 5,6-tetracarboxylic dianhydride;

43. 1-methyl-3-ethyl cyclohexane-3- (1,2) 5,6-tetracarboxylic dianhydride;

44. 1-ethyl cyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride;

45. 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride;

46. 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride;

47. dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride;

48. 4,4'-bisphenol A dianhydride;

49. 1,2,3,4-cyclobutanetetracarboxylic dianhydride; (-)-[1S ^* , 5R ^* , 6S ^* ]-3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3- (tetrahydrofuran-2,5-dione) [That is, (-)-DAN manufactured by JSR Corporation;

50. bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;

51. hydroquinonediphthalic anhydride;

52. ethylene glycol bis (trimelitic anhydride);

53. Miscellaneous.

Other useful dianhydrides include 9,9-disubstituted xanthenes. Such dianhydrides include 9,9-bis- (trifluoromethyl) xanthenetetracarboxylic dianhydride (6FCDA); 9-phenyl-9- (trifluoromethyl) xanthenetetracarboxylic dianhydride (3FCDA); 9,9-diphenyl-2,3,6,7-xantene tetracarboxylic dianhydride (PPXDA); 9,9-diphenyl-2,3,6,7-tetramethylxanthene (TMPPX); 9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic acid bis (p-anisidylimide); 9,9-diphenyl-2,3,6,7-xantene tetracarboxylic bis (butylimide); 9,9-diphenyl-2,3,6,7-xanthenetetracarboxylic acid bis (p-tolylimide); 9-phenyl-9-methyl-2,3,6,7-xantene tetracarboxylic dianhydride (MPXDA); 9-phenyl-9-methyl-2,3,6,7-xanthatetetracarboxylic acid bis (propylimide); 9-phenyl-9-methyl-2,3,6,7-xanthatetetracarboxylic acid bis (p-tolylimide); 9,9-dimethyl-2,3,6,7-xanthatetetracarboxylic dianhydride (MMXDA); 9,9-dimethyl-2,3,6,7-xanthatetetracarboxylic acid bis (propylimide); 9,9-dimethyl-2,3,6,7-xanthenetetracarboxylic acid bis (tolylimide); 9-ethyl-9-methyl-2,3,6,7-xantene tetracarboxylic dianhydride (EMXDA); 9,9-diethyl-2,3,6,7-xantene tetracarboxylic dianhydride (EEXDA); And the like (including Polyimides Based on 9,9-Disubstituted Xanthene Dianhydrides, Trofimenko and Auman, Macromolecules, 1994, vol. 27, p. 1136-1146), which is incorporated herein by reference. It doesn't work.

The above-mentioned tetracarboxylic dianhydrides may be used independently depending on the intended use, or may be used as a mixture of two or more individual dianhydrides. The various dianhydrides mentioned above (but not all) can also be used as their "tetra-acid forms" (or as mono, di, tri or tetra esters of tetra acids), or as their diester acid halides (chlorides) . However, in some embodiments of the present invention, dianhydride forms are generally preferred because they are generally more reactive than acids or esters.

The polyimides and their polyamic acid precursors of the present invention can be prepared using polar organic solvents such as phenol solvent systems or aprotic polar solvent systems. For example, solvents or solvent mixtures based on phenol, phenol, 4-methoxy phenol, 2,6-dimethyl phenol, m-cresol (etc.) can be used. Alternatively, aprotic solvents may also be used alone (or in combination with protic solvents). Some useful solvents include N-methylpyrrolidone (hereinafter referred to as NMP), N, N-dimethylformamide (hereinafter referred to as DMF), N, N-dimethylacetamide (hereinafter referred to as DMAc). ), Dimethyl sulfoxide (hereinafter referred to as DMSO), gamma-butyrolactone, gamma-valerolactone and n-cyclohexyl pyrrolidone. Other useful solvents include chloroform, tetrahydrofuran (hereinafter referred to as THF), cyclohexanone, dioxane, anisole, 2-methoxy ethanol, propylene glycol methyl ether, propylene glycol methyl ether acetate, "cellosolve ( cellosolve) ^TM "(ethylene glycol ethyl ether), butyl" cellosolve ^TM "(ethylene glycol butyl ether)," cellosolve ^TM acetate "(ethylene glycol ethyl ether acetate, Te-byte), and" butyl cellosolve ^TM acetate "(ethylene Glycol butyl ether acetate), propylene glycol, monoethylether acetate, methylmethoxypropionate, lactic acid ethyl ester, and the like. The reaction solvents described above can be used independently or as mixtures.

Alternatively, the solvent systems described above may also be used in combination with aromatic hydrocarbon solvents such as benzene, toluene, xylene or tetralin, these solvents being useful for the removal of water during the imide conversion process. Polyimide resins starting from diamines and tetracarboxylic dianhydrides can be prepared by conventional one-step polymerization reactions known at high temperatures using nearly equivalents (moles) of diamine and tetracarboxylic dianhydride. When using a one-stage polymerization process, the preferred reaction temperature may range from 120 to 350 ° C or from about 150 to 300 ° C. Possible reaction times in the one-stage process can be about 0.5 to 20 hours or about 1 to 15 hours.

The preparation of the polyimide resins of the invention can also be initiated by a two-step polymerization process. In the first step, polyamic acid is synthesized at low temperature. In the second step, the polyamic acid is converted to polyimide at high temperature. When using the two-step polymerization method, polyamic acid synthesis can be carried out at about −10 to 120 ° C. (or about 15 to 100 ° C., or 20 to 80 ° C.), and the reaction time is about 0.5 to 100 hours (or about 1 to 100 hours). Thereafter, the conversion of the polyamic acid to the polyimide may be performed at a reaction temperature of about 120 to 350 ° C. (or about 150 to 300 ° C.) and a reaction time of about 0.5 to 20 hours (or about 1 to 10 hours). .

When using two or more different diamines (or different tetracarboxylic dianhydrides), the polymer reaction method is typically not limited (ie, various reaction methods may be used). For example, one reaction method can be used to mix all of the starting materials followed by polymerization, which is particularly useful when aiming for random polyimide resins. In an alternative reaction method, two or more diamines or tetracarboxylic dianhydrides are added sequentially and the monomers are added to the reaction vessel in a controlled manner, which method is useful for preparing block or segmented polyimide resins. can do.

In another embodiment, when the polyimide backbone is soluble, a soluble polyimide resin solution can be obtained, and the soluble polyimide resin can be formed by removing the solvent. The purified soluble polyimide resin can be obtained by the precipitation method of precipitating the above-mentioned polyimide from the polyimide resin solution using a poor solvent. This polyimide resin can be further purified and then dissolved again in a polyimide solution in an organic solvent (or mixture of organic solvents) with the desired polarity and then used as a soluble polyimide.

The polyimide of the present invention can be prepared using a variety of different methods depending on the manner in which the components (ie, monomer and solvent) are introduced into each other. Various methods of preparing the polyamic acid solution are as follows.

(a) A method of first mixing the diamine component and the dianhydride component together, and then adding the mixture partly to the solvent with stirring.

(b) adding a solvent to the stirring mixture of diamine and dianhydride components (as opposed to (a) above).

(c) dissolving only diamine in a solvent and then adding thereto an dianhydride in a proportion to control the reaction rate.

(d) dissolving only the dianhydride component in a solvent, and then adding the amine component therein at a rate such that the reaction rate is controlled.

(e) The diamine component and the dianhydride component are dissolved in a solvent separately, and then these solutions are mixed in a reactor.

(f) first forming a polyamic acid with excess amine component and another polyamic acid with excess dianhydride component, and then reacting with each other in a manner such that a non-random or block copolymer is produced, in particular in the reactor.

(g) first reacting a certain proportion of the amine component and the dianhydride component and then reacting the remaining diamine component or vice versa.

(h) A method in which the components are added in part or in part to any or all of the solvent in any order, and any or all of the optional components are added to the part or all of the solvent as a solution.

(i) first reacting one of the dianhydride components with one of the diamine components to form a first polyamic acid, and then reacting the remaining dianhydride components with the remaining amine components to form a second polyamic acid, and then forming a film. Combining the amic acid in a number of arbitrary ways before.

In general, the polyamic acid casting solution may be derived from any one of the methods of preparing the polyamic acid solution described above.

The polyamic acid casting solution of the present invention comprises a polyamic acid solution in combination with a portion of the conversion chemical. Conversion chemicals useful in the present invention include (i) one or more dehydrating agents, such as aliphatic acid anhydrides (such as acetic anhydride) and aromatic acid anhydrides; And (ii) one or more catalysts such as aliphatic tertiary amines (such as triethylamine), aromatic tertiary amines (such as dimethylaniline) and heterocyclic tertiary amines (pyridine, picoline, isoquinoline, etc.) It is not limited to these. Anhydride dehydrating materials are typically used in slightly molar excess of the amount of amic acid groups present in the polyamic acid solution. The amount of acetic anhydride used is typically about 2.0 to 3.0 moles / equivalent polyamic acid. Generally, similar amounts of tertiary amine catalysts are used. Alternatively, a thermal conversion process, i.e., a process using only heat to cure the polyimide from the polyamic acid precursor state, may be used.

During the conversion to polyimide, water is typically produced because of the “opening” of the polyamic acid precursor material. Water may be removed in a process that facilitates further conversion of acid to imide. Water removal can be accomplished by azeotropic distillation with benzene, toluene, xylene, tetralin, or other suitable agent capable of removing water from the reaction system. Alternatively, dehydrating agents (eg, acetic anhydride or molecular sieves) can be used to accelerate the conversion of polyamic acid to polyimide. Optionally, an imidization catalyst can be added to the reaction mixture. Typical basic imidation catalysts useful in the present invention include, for example, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, isoquinoline, α-picoline, β-picolin, γ-picoline , 2,4-rutidine, triethylamine, tributylamine, tripentylamine, N-methylmorpholine and the like. Other typical imidization catalysts include benzoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenyl acetic acid, 4-hydroxyphenylpropylene acid , Phosphoric acid, p-phenol sulfonic acid, p-toluene sulfonic acid, crotonic acid and the like. The loading level of the imidization catalyst described above should be 1 to 50 mol%, or 5 to 35 mol%, based on the diamine or the mixture of diamines. The polymerization reaction using these condensation polymerization catalysts can be performed at low temperature. This protocol can be advantageous if it avoids coloring and the reaction time is shortened.

In one embodiment of the invention, the polyimide film has 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250 and 300 microns Are formed to have a thickness between any two numbers (including any two numbers). Typically, the glass transition temperature of the polyimide of the present invention is about 250 ° C., especially when derived from BPDA as a dianhydride component. In many cases, the glass transition temperatures of the polyimides of the invention range between any two numbers of 200, 220, 240, 260, 280, 300, 320 and 360 ° C.

In one embodiment of the invention, the polyimide has a glass transition temperature of 550, 530, 510, 490, 470, 450, 430, 410, 390, 370, 350, 330, 310, 290, 270, 250, 220, 200 , And between any two numbers of 150 and 100 ° C. and in a range including them.

In one embodiment of the invention, fillers may be added to the polyimide formulation to form polyimide complexes. Some fillers include aluminum oxide, silica, boron nitride, boron nitride coated aluminum oxide, granular alumina, granular silica, fumed silica, silicon carbide, aluminum nitride, aluminum oxide coated aluminum nitride, titanium dioxide , Dicalcium phosphate, barium titanate, barium strontium titanate (BST), lead zirconate titanate (PZT), lead lanthanum titanate, lead lanthanum zirconate titanate (PLZT), lead magnesium niobate (PMN) Calcium copper titanate, carbon powder, titanium dioxide, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, silicon carbide, diamond, dicalcium phosphate, polyaniline, polythiophene, polypyrrole, polyphenylenevinylene, Polydialkylfluorenes, and electrically conductive polymers and these It includes, but the combination is not limited to these. In one embodiment, the nano-sized filler (ie, alumina oxide particles) is first dispersed in a solvent to form a slurry in accordance with the present invention. The slurry is then dispersed in a polyamic acid precursor solution. This mixture is referred to herein as a filled polyamic acid casting solution. The concentration of filler in the polyimide (in the final composite film) is typically 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85% by weight. As the concentration of filler increases, the thermal conductivity of the composite polyimide also increases. Here, the filler may be present at about 1, 3, 5, 7, 9 or 10% by weight to about 15, 20, 25, 30, 35, 40, 45 or 50% by weight or more, generally having an average particle size ( Polyimide binder matrix) between any two numbers of 100, 125, 150, 175, 200, 250, 300, 350, 400, 450, 500, 1000, 2000, 3000, 4000, and 5000 nanometers or any It may range from two numbers, and the particle size of at least 80, 85, 90, 92, 94, 95, 96, 98, 99 or 100% by weight of the dispersed filler is within the size range defined above.

It is not possible to discuss or describe methods of making all possible polyimide-metal laminates useful in the practice of the present invention. It should be understood that the monomer system of the present invention may provide the advantages described above in various methods of preparation. The compositions of the present invention can be prepared as described herein and can be readily prepared by one of skill in the art in any one method, using any conventional or non-conventional polyimide (and multilayer) manufacturing technique. .

A conductive layer (typically a metal) can be formed on the polyimide of the present invention by the following method.

i. Metal sputtering (optionally, then electroplating);

ii. Foil lamination; And / or

iii. Any conventional or non-conventional method of applying a thin metal layer to a substrate.

Conductive layers as used herein include copper, steel (including stainless steel), metal alloys derived from aluminum, brass, copper alloys, copper and molybdenum, Kovar®, Invar®, bimetals, hemp Metal may be selected from the group consisting of metals, two layers of copper and trimetals derived from one layer of Invar®, and three metals derived from two layers of copper and molybdenum of one layer.

In one embodiment of the invention, the high Tg polyimide layer is disposed between the conductive layers. Optionally, a low Tg polyimide layer can be used to join the metal and the high Tg layer. Typically, high Tg layers can be used to improve the structural integrity of the laminate and / or stability against environmental changes (eg, heat and humidity). Electronic circuitry (limited to or connected to or integrated with a metal layer) may exhibit improved low (signal) loss in high speed digital products.

In another embodiment of the invention, the low Tg polyimide layer is disposed between the conductive layer and the high Tg polyimide layer, and the second low Tg polyimide layer is disposed opposite the high Tg polyimide. One advantage of this type of structure is that the lamination temperature of the multilayer substrate is lowered to the lamination temperature necessary for bonding the low Tg polyimide layer. In one embodiment, the low Tg and high Tg layers are cast simultaneously as one polyamic acid film and then cured to form a three layer polyimide. In another embodiment, the high Tg layer is bonded to the metal using an adhesive made from epoxy, cyanate, urethane, melamine, acrylic, phenol, phenol butyral, imide or combinations thereof.

In one embodiment of the invention, the polyimide disclosed herein may be used to form polyimide fibers. In addition, the polyimide may be used herein to form molded parts. These polyimides can be extruded to form gaskets, rings, diaphragms, mechanical components and components, wire coatings, and the like.

In one embodiment of the invention, the polyimide of formula (9) is formed.

<Formula 9>

Typically, the polyimide of formula 9 is formed from a mixture of isomeric diamines based on the mixtures (and isomers) described above. Another general polyimide of the present invention may be represented by the following formula (10).

<Formula 10>

The polyimide film of the present invention can exhibit not only high Tg but also excellent light transmittance. These two properties make polyimide films useful for making flexible substrates in organic light emitting diode (OLED) displays or liquid crystal displays (LCDs). These polyimides may also be useful in coatings for other electronic products, such as electronic components (eg IC's). Other useful products include, but are not limited to, optoelectronic materials (eg, absence of liquid crystal substrates), color filter blanket films, electronic switches for optical reaction systems, integrated circuit chip stress buffers, interlayer dielectrics, or materials for optical fibers. It doesn't work.

In another embodiment of the present invention, when combining the diamine of formula (2) with other diamines generally disclosed, other physical properties of the polyimide may be improved. One physical property of particular importance in many products is adhesiveness. This property can be improved especially when the diamine substituent is diaminosiloxane. Polyimide of the present invention, partially derived from diaminosiloxanes, may be dissolved in low boiling solvents such as cyclohexanone, dioxane, and lactic acid ethyl esters. This makes it possible to form polyimide films with good adhesion to silicon wafers (ie, generally without sacrificing light transmission and thermal stability) while maintaining relatively low processing temperatures.

The following examples illustrate the invention in detail, but the invention is not limited to these examples.

Example

Measurements of various physical properties are recorded in the examples below. In the case of glass transition temperature, TA apparatus 2910 DSC was used by the differential scanning calorimeter (DSC) method. 5-10 mg of sample was placed in an unsealed sample pan. The test was conducted at a rate of 10 ° C./min from ambient temperature to 400 ° C. under a N ₂ flow of 50 ml / min. For light transmittance (T%), transmittance data was obtained using a Cary 500 UV / VIS / NIR spectrometer (Varian). Spectra of 200 nm to about 700 nm were controlled under the air background. The coefficient of thermal expansion (CTE) of these samples was analyzed using a Thermo Mechanical Analyzer (TMA). The instrument can read the dimensional change of the film sample as it is heated. During the test, the film was kept under a constant load of about 0.05 N. CTE for each film sample was determined by performing a linear regression of the data obtained at a temperature of about 50 ° C to 250 ° C. The film thickness in the measurements was about 3.3 to about 4.3 mils and was calculated on a 4.0 mil basis (or about 100 microns).

Example  One

In a 250-ml two-neck flask with N ₂ blanket, 38.88 g of pyromellitic dianhydride (PMDA) was dissolved in 120 ml of DMAc with mechanical stirring. Then, 2,5- (or 6) -bis (aminomethyl) -2-methyl-bicyclo [2.2.1] heptane (k = 0, i.e., the diamine represented by Formula 2, Formulas 6 and 7 30.0 g were mixed with 40 ml of DMAc and then added dropwise to the flask over 3 hours, during which time the reaction mixture was kept at about 0 ° C. This solution was polymerizable into a viscous polymer.

The reaction mixture was kept at room temperature overnight. Initial precipitation was observed, but the precipitate dissolved slowly by stirring. The mixture eventually became a clear viscous solution.

Thereafter, the reaction mixture was heated to 35 ° C. for about 72 hours. At this temperature, most but not all of the precipitate was completely dissolved. A portion of the reaction solution was cast on a 5 "X 7" glass slide using a 10-mil thick blade. The glass slide with the polymer film was maintained at room temperature under vacuum for about 3 hours. Polyimide films were prepared from these slides.

Additional polymer reaction mixture was added to acetone. The resulting precipitated polymer (polyamic acid) was filtered off and then dried under vacuum overnight at room temperature. A portion of the polyamic acid was coated on a 5 "X 7" glass slide. From this, the vacuumed polymer (PAA) film (on a glass slide) was placed in an (N ₂ purging) oven at a temperature profile of 60 ° C. (1 hour), 100 ° C. (1 hour) and 200 ° C. (1 hour) The mid film was formed. DMAc and water were purged from the oven by a continuous N ₂ feed.

After cooling to about 50 ° C., the polyimide film was removed from the oven and then the glass substrate (with the film) was immersed in boiling water to separate from the glass substrate. The separated polyimide film was placed in a vacuum oven at 300 ° C. and cured for about 1 hour under vacuum. Film properties are listed in Table 1 below.

Example  2

In a 50-ml three-neck flask with N ₂ blanket, 9.8 g of pyromellitic dianhydride (PMDA) was dissolved in 35 ml of DMAc using a magnetic stirrer. Next, 10.5 g of 2,5 (or 6) -bis (aminomethyl) -2-methyl-bicyclo [2.2.1] heptane (ie k = 1) was added with dilution with 10 ml of additional DMAc. . The polymerization reaction was maintained at 0 ° C. for about 1 hour. Precipitation was observed. The mixture was kept at room temperature overnight. The reaction mixture was then maintained at 60 ° C. for about 72 hours. A portion of the reaction solution was cast on a 5 x 7-cm glass slide and maintained at room temperature under vacuum for about 3 hours. This released the trapped bubbles.

The cast polymer was then converted to a polyimide film. The temperature for this conversion was adjusted according to 60 ° C. (1 hour), 100 ° C. (1 hour), 200 ° C. (1 hour). As a result of the conversion, most of the DMAc and water was purged under continuous N ₂ feed. After the film was cooled (to about 50 ° C.), the film substrate was taken out of the oven. The polyimide film was separated from the glass substrate by impregnating the glass substrate (and film) in boiling water. The separated polyimide film was placed in a vacuum oven set at 300 ° C. and further cured for 1 hour. Film properties are listed in Table 1 below.

Example  3

In a 250-ml two-neck flask with N ₂ blanket, 43.7 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was dissolved in 120 ml of DMAc with magnetic stirring. Next, 25.0 g of 2,5- (or 6) -bis (aminomethyl) -2-methyl-bicyclo [2.2.1] heptane (ie k = 0) are dissolved in 40 ml of DMAc, and through an addition furnace The flask was added dropwise over 3 hours, during which time the entire flask was kept at approximately 0 ° C. A mechanical stirrer was used. After all diamine / DMAc was added, the entire mixture became off-white high viscosity. The reaction was kept at 30 ° C. overnight. The large mass was dissolved overnight and the entire mixture became a slightly light yellow transparent viscous liquid. Undissolved solids were rarely observed. Thereafter, the reaction was maintained at 35 ° C. for 72 hours (or until all the precipitates were substantially dissolved). The reaction mixture remained light yellow, transparent and relatively homogeneous.

A portion of the reaction solution was cast using a 10-mil blade on a 5 "X 7" glass slide. The cast polymer was kept under vacuum at room temperature for about 3 hours to remove the trapped bubbles.

The pre-vacuum polymer was placed in an N ₂ purged oven to convert the cast polyamic acid film to a polyimide film. The temperatures were set at 60 ° C. (1 hour), 100 ° C. (1 hour) and 200 ° C. (1 hour). Excess DMAc and water were purged from the oven by continuous feeding of the N ₂ stream.

After cooling to approximately 50 ° C., the film substrate on the glass was removed from the oven. The polyimide film was separated from the glass substrate by impregnating the glass (and film) in boiling water. The separated polyimide film was placed in a vacuum oven at 300 ° C. and cured under vacuum for about 1 hour. The final polyimide obtained had good mechanical integrity and showed a bright yellow color. Film properties are listed in Table 1 below.

Comparative example  One

In a 250-ml two-neck flask with N ₂ blanket, 41.44 g of pyromellitic dianhydride (PMDA) was dissolved in 120 ml of DMAc with mechanical stirring. Next, norbornane diamine (NBDA diamine, manufactured by Mitsui Chemicals, Ltd., a mixture of diamines containing 2,5-NBDA and 2,6-NBDA, IUPAC name is 2,5 (and 6) -bis ( 29.31 g of aminomethyl) bicyclo [2.2.1] heptane was diluted with 40 ml of DMAc. The diamine solution was then added dropwise to the dianhydride solution via the addition furnace over 3 hours, during which the temperature was maintained at about 0 ° C.

After all of the diamine solution had been added, the mixture became viscous and pinkish. The polymerization reaction was kept at room temperature overnight. Some precipitation was observed and dissolved overnight. The mixture became a yellowish clear viscous liquid. The polymer was then aged for 72 hours at 35 ° C. until all precipitate dissolved.

A portion of the polymer was cast using a 10-mil blade on a 5 "X 7" glass slide. Casting under vacuum at room temperature for about 3 hours removed the trapped bubbles.

Precast vacuum polymer (polyamic acid) was placed in an oven (N ₂ purging), set at a temperature of about 60 ° C. (1 hour), 100 ° C. (1 hour) and 200 ° C. (about 1 hour), and polyimide A film was formed. DMAc and water were purged from the oven by a continuous supply of nitrogen stream.

After cooling to about 50 ° C., the substrate was removed from the oven and the glass substrate (and film) was impregnated with boiling water to separate the film from the glass substrate.

The polyimide film was placed in a vacuum oven at 300 ° C. and thermally cured for 1 hour. The final polyimide obtained was yellow in color and had good physical integrity. Film properties are listed in Table 1 below.

PI film properties Example 1 Example 2 Example 3 Comparative Example 1 % Light transmittance (400 to 700 nm) 85.4 49.5 84.1 45.0 CTE (ppm / ℃) 51.9 58.8 51.9 61.0 Tg (DMA) 355.6 ℃ 326.1 ℃ 255.5 ℃ 324.2 ℃

The polyimide derived from the reaction product of the diamine component and the dianhydride component according to the present invention has a glass transition temperature, light transmittance and coefficient of thermal expansion suitable as a glass substitute for certain electronic products.

Claims (9)

Polyimide of formula (1). <Formula 1>

In the formula, R is -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -CH ₃ ,-(CH ₂ ) ₄ -CH ₃ , -CX ₃ , -CH ₂ -CX ₃ , -CH ₂ -CH ₂ -CX ₃ ,-(CH ₂ ) ₃ -CX ₃ ,-(CH ₂ ) ₄ -CX ₃ , where X is F, Cl or Br, -C ₆ H ₅ (a 6-membered aromatic ring) and C ₆ H ₅ -CH ₃ , wherein the methyl group is in the ortho or para position in the 6-membered aromatic ring, R ₁ is a tetravalent group having 4 to 27 carbon atoms and is an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group, a polycyclic aromatic group, a substituted aliphatic or aromatic group (e.g., fluorine ), From the group comprising non-condensed polycyclic aliphatic groups or aromatic groups (or mixtures thereof) condensed aromatic groups, and / or cyclic aliphatic groups or aromatic groups connected to one another directly or via a bridging group. Selected, k is any integer of 0, 1, and 2, n is an integer between any two numbers of 10, 100, 1000, 10,000 and 100,000. Polyimide of the formula (11). <Formula 11>

In the formula, R ₁ is a tetravalent group having 4 to 27 carbon atoms and is an aliphatic group, a monocyclic aliphatic group, a condensed polycyclic aliphatic group, a monocyclic aromatic group, a polycyclic aromatic group, a substituted aliphatic or aromatic group (e.g., fluorine ), A condensed aromatic group, and / or a cyclic aliphatic group or aromatic group is selected from the group comprising non-condensed polycyclic aliphatic groups or aromatic groups (or mixtures thereof) linked to each other directly or via a crosslinking group k is any integer of 0, 1, and 2, n is an integer between any two numbers of 10, 100, 1000, 10,000 and 100,000. The diamine component is represented by the following formula (2), the dianhydride component is selected from the group consisting of dianhydride, diacid-diester, diacid halide ester, or tetra-carboxylic acid, diamine component and dianhydride Polyamic acid derived from the reaction product of the water component. <Formula 2>

In the formula, R is -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -CH ₃ ,-(CH ₂ ) ₄ -CH ₃ , -CX ₃ , -CH ₂ -CX ₃ , -CH ₂ -CH ₂ -CX ₃ ,-(CH ₂ ) ₃ -CX ₃ ,-(CH ₂ ) ₄ -CX ₃ , where X is F, Cl or Br, -C ₆ H ₅ (a 6-membered aromatic ring) and C ₆ H ₅ -CH ₃ , wherein the methyl group is in the ortho or para position in the 6-membered aromatic ring, k is any integer of 0, 1, and 2. The diamine component is 2,5- (or 6) -bis (aminomethyl) -2-methylbicyclo [2.2.1] heptane and the dianhydride component is an dianhydride, diacid-diester, diacid halide ester or tetra-carboxyl A polyamic acid derived from the reaction product of a diamine component and a dianhydride component, selected from the group consisting of acids. The diamine component comprises a diamine represented by the following formula (2) in the range between any two numbers of 3, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50 mol%, The diamine represented is included in the range between any two numbers of 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and 97 mol%, and the dianhydride component is a dianhydride, diacid-diester. A polyamic acid composition derived from a diamine component and a dianhydride component, selected from the group consisting of diacid halide ester or tetra-carboxylic acid. <Formula 2>

<Formula 12> NH ₂ -X ₁ -NH ₂ In the formula, R is -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -CH ₃ ,-(CH ₂ ) ₄ -CH ₃ , -CX ₃ , -CH ₂ -CX ₃ , -CH ₂ -CH ₂ -CX ₃ ,-(CH ₂ ) ₃ -CX ₃ ,-(CH ₂ ) ₄ -CX ₃ , where X is F, Cl or Br, -C ₆ H ₅ (a 6-membered aromatic ring) and C ₆ H ₅ -CH ₃ , wherein the methyl group is in the ortho or para position in the 6-membered aromatic ring, k is any integer of 0, 1, and 2, X ₁ represents a divalent alicyclic group, a divalent aliphatic group, a divalent aromatic group, a substituted divalent aliphatic group, a substituted divalent aromatic group, or a divalent siloxane-containing aliphatic or aromatic group. The composition of claim 5, wherein said composition is thermally or chemically imidated to form a polyimide. Having a thickness between any two of 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, and 300 microns Polyimide according to claim 2 or 6 in the form of a film. 8. The composition of claim 7, wherein the composition comprises aluminum oxide, silica, boron nitride, boron nitride coated aluminum oxide, granular alumina, granular silica, fumed silica, silicon carbide, aluminum nitride, aluminum oxide coated aluminum nit. Ride, titanium dioxide, dicalcium phosphate, barium titanate, barium strontium titanate (BST), lead zirconate titanate (PZT), lead lanthanum titanate, lead lanthanum zirconate titanate (PLZT), lead magnesium nio Bate (PMN), calcium copper titanate, carbon powder, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, silicon carbide, diamond, dicalcium phosphate, polyaniline, polythiophene, polypyrrole, polyphenylenevinylene , Polydialkylfluorenes, and electrically conductive polymers and combinations thereof Polyimide film further comprising a filler selected from the group consisting of. The polyimide film of claim 8 wherein the filler is doped with a metal dopant selected from Groups III, IV, V, and VI of the periodic table.