Granted Patent B2

US 9,161,440 · App. 11/758,773 · Granted Oct 13, 2015

Abstract

Claims (115)

1. An article comprising a solvent cast film, the film comprising

a thermoplastic polyimide consisting essentially of structural units derived from polymerization of

a dianhydride component comprising at least 80 mole % of a dianhydride selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, based on the total moles of dianhydride with

a diamine component consisting of at least 80 mole % p-phenylenediamine based on the total moles of the diamine component and up to 20 mole % of a diamine selected from the group consisting of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, and combinations thereof;

wherein the dianhydride component and the diamine component are in a molar ratio of from 1 to 1.3 moles diamine per mole of dianhydride;

wherein the polyimide has a glass transition temperature of 190° C. or greater;

wherein the film has

a coefficient of thermal expansion of less than 30 ppm/° C. measured over 30° C. to 200° C.,

a thickness from 0.1 to 250 micrometers, and

less than 5% residual solvent by weight;

wherein the polyimide has less than 15 molar % of structural units derived from a member of the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and a combination thereof; and

wherein the film further comprises an exfoliated nanoclay and has a lower CTE (measured over 30° C. to 200° C.) than a film of the same composition without the exfoliated nanoclay.

2. The article of claim 1 , wherein the glass transition temperature of the polyimide is from 190° C. to 500° C.

3. The article of claim 1 , wherein the dianhydride component further comprises a dianhydride selected from the group consisting of:

2,2′-bis(1,3-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-methyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-phenyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-trifluoromethyl-2-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-trifluoromethyl-3-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;

2,2-bis((4-(3,3-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride;

2,2-bis((4-(3,3-dicarboxyphenoxy)phenyl)propane dianhydride;

2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;

2,2′-dibromo-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,3,6,7-naphthalic dianhydride;

3,3′,4,4′-benzophenonetetracarboxylic dianhydride;

3,3′,4,4′-biphenylethertetracarboxylic dianhydride;

3,3′,4,4′-biphenylsulphonictetracarboxylic dianhydride;

3,3′,4,4′-biphenyltetracarboxylic dianhydride;

3,3′,4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride;

3,3′,4,4′-diphenylmethane tetracarboxylic dianhydride;

3,3′,4,4′-diphenylsulfide tetracarboxylic dianhydride;

3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride;

3,3′,4,4′-diphenylsulfoxide tetracarboxylic dianhydride;

3,3′-benzophenone tetracarboxylic dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulphone dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;

4,4′-bisphenol A dianhydride;

4,4′-carbonyldiphthalic anhydride;

6,6′-bis(3,4-dicarboxyphenoxy)-2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]dianhydride;

7,7′-bis(3,4-dicarboxyphenoxy)-3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2H-1-benzopyran]dianhydride;

bis(phthalic)phenylsulphineoxide dianhydride;

bis(triphenylphthalic)-4,4′-diphenylether dianhydride;

bis(triphenylphthalic)-4,4′-diphenylmethane dianhydride;

hydroquinone diphthalic anhydride;

m-phenylene-bis(triphenylphthalic)dianhydride;

p-phenylene-bis(triphenylphthalic)dianhydride;

pyromellitic dianhydride;

(3,3′,4,4′-diphenyl)phenylphosphine tetracarboxylic dianhydride;

(3,3′,4,4′-diphenyl)phenylphosphineoxide tetracarboxylic dianhydride;

1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride;

1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride;

1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride;

1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride; and a combination thereof.

4. The article of claim 1 , wherein the film comprises a combination of diamines sufficient to impart a CTE (measured over 30° C. to 200° C.) to the film that remains constant while the combination of diamines also imparts a Tg to the film from 220° C. to 375° C.

5. The article of claim 1 , wherein the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and a combination thereof.

6. The article of claim 5 , wherein the film has a Tg that is the same as a film of the same composition without the nanoclay.

7. The article of claim 5 , wherein the film is transparent.

8. The article of claim 1 , wherein the film has a coefficient of thermal expansion of at least 5 ppm/° C. measured over 30° C. to 200° C.

9. The article of claim 1 , wherein the film has a coefficient of thermal expansion of 5 ppm/° C. to 30 ppm/° C. measured over 30° C. to 200° C.

10. The article of claim 1 , wherein the film has a coefficient of thermal expansion of 10 ppm/° C. to 30 ppm/° C. measured over 30° C. to 200° C.

11. The article of claim 1 , wherein the film has a coefficient of thermal expansion of 10 ppm/° C. to 20 ppm/° C. measured over 30° C. to 200° C.

12. The article of claim 1 , wherein the film has a coefficient of thermal expansion that is within ±20 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer.

13. The article of claim 1 , wherein the film has a coefficient of thermal expansion that is within ±15 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of copper.

14. The article of claim 1 , wherein the film loses less than 5% of its initial weight after storage in water for 24 hours at 25° C.

15. The article of claim 1 , wherein the film loses less than 2% of its initial weight after storage in water for 24 hours at 25° C.

16. The article of claim 1 , wherein a 10 wt % solution of the dried film in dimethylacetamide or N-methylpyrolidinone has an inherent viscosity of greater than 0.05 dl/g.

17. The article of claim 1 , wherein the film after lamination to a substrate at a temperature from 250 to 450° C. has a coefficient of thermal expansion within ±10 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of the film prior to lamination.

18. The article of claim 1 , wherein the film further comprises a recycled polyimide.

19. The article of claim 18 , wherein the film comprises up to 50 wt % of a recycled polyimide, wherein prior to recycling the recycled polyimide has a glass transition temperature from 210° C. to 450° C.

20. The article of claim 18 , wherein the film comprises up to 30 wt % of a recycled polyimide film, wherein prior to recycling the recycled polyimide film has a glass transition temperature from 210° C. to 450° C.

21. The article of claim 18 , wherein the coefficient of thermal expansion of the film comprising the recycled polyimide is within ±10 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of a film having the same composition without the recycled polyimide.

22. The article of claim 18 , wherein the film comprising the recycled polyimide is capable of being melt blended.

23. The article of claim 1 , wherein the film is cast from a composition comprising 1 to 30 wt % solids.

24. The article of claim 1 , wherein the polyimide film is disposed on a substrate.

25. The article of claim 24 , wherein the substrate is selected from the group consisting of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, and a polymer.

26. The article of claim 24 , further comprising a second substrate disposed on a side of the film opposite the first substrate.

27. The article of claim 26 , wherein the second substrate is selected from the group consisting of copper, silicon, aluminum, gold, silver, nickel, glass, ceramic, a polymer, and a combination thereof.

28. The article of claim 1 , wherein the article is a laminate further comprising a conductive layer comprising a metal, wherein the film is adheringly disposed on a face of the conductive layer.

29. The article of claim 28 , wherein the metal is copper, silver, gold, aluminum, or an alloy comprising at least one of the foregoing metals.

30. The article of claim 1 , wherein the article is a flexible printed circuit comprising a copper layer adheringly disposed on the polyimide film.

31. The article of claim 30 , wherein the flexible printed circuit further comprises a dielectric layer comprising a second material other than the polyimide of the film.

32. The article of claim 1 , wherein the article is a capacitor comprising the polyimide film disposed between a first metal substrate and a second metal substrate.

33. The article of claim 1 , further comprising an electrically conductive wire substrate, wherein the polyimide film surroundingly coats at least a portion of a surface of the wire.

34. A method of manufacture of the article of claim 1 , comprising forming the solvent cast polyimide film on a substrate.

35. An article comprising a solvent cast polyetherimide film, the film comprising:

a thermoplastic polyetherimide consisting essentially of structural units derived from the polymerization of

a dianhydride component comprising at least 80 mole % of a dianhydride selected from the group consisting of 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4′-oxydiphthalic anhydride, and combinations thereof, based on the total moles of dianhydride, with

a diamine component consisting of at least 80 mole % p-phenylenediamine based on the total moles of diamine and up to 20 mole % of a diamine selected from the group consisting of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, and combinations thereof;

wherein the polyetherimide comprises less than 15 mole % of structural units selected derived from the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and combinations thereof;

wherein the dianhydride component and the diamine component are in a molar ratio of from 1 to 1.3 moles diamine per mole of dianhydride;

wherein the polyetherimide has a glass transition temperature from 190° C. to 400° C., and

wherein the film has

a coefficient of thermal expansion of less than 30 ppm/° C. measured over 30° C. to 200° C.,

a thickness from 0.1 to 250 micrometers, and

less than 5% residual solvent by weight;

wherein the film has a coefficient of thermal expansion that is within ±20 ppm/° C. (measured over 30° C. to 200° C.) of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer;

wherein the film further comprises an exfoliated nanoclay and has a lower CTE (measured over 30° C. to 200° C.) than a film of the same composition without the exfoliated nano clay; and

wherein the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, phenol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and combinations thereof.

Assignments (9)