Composition containing carbon nanotubes having coating thereof and process for producing them

• US 20060052509A1
• Filed: 10/31/2003
• Published: 03/09/2006
• Est. Priority Date: 11/01/2002
• Status: Active Grant

• Current Assignee: Mitsubishi Chemical Corporation (Mitsubishi Chemical Group Corp.)
• Original Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Inventors: Saitoh, Takashi
• Granted Patent: US 7,645,400 B2
• Time in Patent Office: Days
• US Class Current: 524/496
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08G 2261/1424 containing ether groups, including alkoxy
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/512 Hole transport
• CPC Class Codes: C08G 2261/794 with polymeric dopants
• CPC Class Codes: C08K 3/041 Carbon nanotubes
• CPC Class Codes: C08L 25/18 Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• CPC Class Codes: C08L 33/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 65/02 Polyphenylenes
• CPC Class Codes: C08L 79/02 Polyamines
• CPC Class Codes: C09D 165/00 Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C09D107/00 - C09D157/00, C09D161/00 take precedence; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 17/005 Carbon black
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01G 9/028 Organic semiconducting electrolytes, e.g. TCNQ
• CPC Class Codes: Y10S 977/742 Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/745 having a modified surface
• CPC Class Codes: Y10S 977/746 Modified with biological, organic, or hydrocarbon material
• CPC Class Codes: Y10S 977/753 with polymeric or organic binder
• CPC Class Codes: Y10T 428/24994 : Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

The object of the present invention is to provide a carbon nanotube composition that does not impair the characteristics of the carbon nanotubes itself, allows the carbon nanotubes to be dispersed or solubilized in a solvent, does not cause separation or aggregation of the carbon nanotubes even during long-term storage, has superior electrical conductivity, film formability and moldability, can be easily coated or covered onto a base material, and the resulting coated film has superior moisture resistance, weather resistance and hardness; a composite having a coated film composed thereof; and, their production methods. In order to achieve this object, the present invention provides a carbon nanotube composition that contains a conducting polymer (a) or heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c), and may additionally contain a high molecular weight compound (d), a basic compound (e), a surfactant (f), a silane coupling agent (g) and colloidal silica (h) as necessary; a composite having a coated film composed of the composition; and, their production methods.

Claims

1. A carbon nanotube composition that contains a conducting polymer (a), a solvent (b) and carbon nanotubes (c).

3. A carbon nanotube composition according to claim 1, wherein the carbon nanotube composition additionally contains a high molecular weight compound (d).

4. A carbon nanotube composition according to claim 1, wherein the carbon nanotube composition additionally contains a basic compound (e).

5. A carbon nanotube composition according to claim 1, wherein the carbon nanotube composition additionally contains a surfactant (f).

6. A carbon nanotube composition according to claim 1, wherein the carbon nanotube composition additionally contains a silane coupling agent (g) represented by the following formula (1):

7. A carbon nanotube composition according to claim 1, wherein the carbon nanotube composition additionally contains a colloidal silica (h).

8. A carbon nanotube composition according to claim 1, wherein the conducting polymer (a) is a water soluble conducting polymer.

9. A carbon nanotube composition according to claim 8, wherein the water soluble conducting polymer has at least one of a sulfonic acid group and a carboxyl group.

10. A carbon nanotube composition according to claim 9, wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer that contains 20 to 100% of at least one type of the repeating units selected from the following formulas (2) to (10) relative to the total number of repeating units throughout the entire polymer:

11. A carbon nanotube composition according to claim 9, wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer that contains 20 to 100% of the repeating unit represented by the following formula (11) relative to the total number of repeating units throughout the entire polymer:

12. A carbon nanotube composition according to claim 9, wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is represented by the following formula (12):

13. A carbon nanotube composition according to claim 9, wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer obtained by polymerizing at least one of type of acidic group-substituted aniline represented by the following formula (13), its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound:

14. A carbon nanotube composition according to claim 9, wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is a water soluble conducting polymer obtained by polymerizing at least one type of alkoxy group-substituted aminobenzene sulfonic acid, its alkaline metal salt, ammonium salt and substituted ammonium salt, with an oxidizing agent in a solution containing a basic compound.

15. A carbon nanotube composition according to claim 9, wherein the water soluble conducting polymer having at least one of a sulfonic acid group and a carboxyl group is polyethylene dioxythiophene polystyrene sulfate.

22. A production method of a carbon nanotube composition comprising:

irradiating a carbon nanotube composition according to claim 1 with ultrasonic waves and mixing.

23. A composite comprising a base material, and a coated film composed of the carbon nanotube composition according to claim 1 on at least one surface of the base material.

24. A method of producing a composite comprising:

coating the carbon nanotube composition according to claim 1 onto at least one surface of a base material, and forming a coated film by allowing the coated carbon nanotube to stand at room temperature or subjecting it to heat treatment.

25. A production method of a composite according to claim 24, wherein the heat treatment is carried out within a temperature range of normal temperature to 250°

C.

2. A carbon nanotube composition that contains a heterocyclic compound trimer (i), a solvent (b) and carbon nanotubes (c).

16. A carbon nanotube composition according to claim 2, wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following formula (16):

17. A carbon nanotube composition according to claim 2, wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following general formula (17):

18. A carbon nanotube composition according to claim 2, wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following general formula (18):

19. A carbon nanotube composition according to claim 2, wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer represented by the following general formula (19):

20. A carbon nanotube composition according to claim 2, wherein the composition contains a heterocyclic compound trimer (i) that is a heterocyclic compound trimer obtained by reacting at least one type of heterocyclic compound represented by the following general formula (20) in a reaction mixture containing at least one type of oxidizing agent and at least one type of solvent:

21. A carbon nanotube composition according to claim 2, wherein said carbon nanotube composition includes a the heterocyclic compound trimer (i) has having a layered structure.