Conductive polymer material and substrate

Patent metadata

Field	Value
Publication number	US-9666327-B2
Application number	US-201514827915-A
Country	US
Kind code	B2
Filing date	Aug 17, 2015
Priority date	Sep 11, 2014
Publication date	May 30, 2017
Grant date	May 30, 2017

Abstract

The present invention provides a conductive polymer material including (A) a π-conjugated polymer, (B) a dopant polymer which contains a repeating unit having a sulfo group and has a weight-average molecular weight in the range of 1,000 to 500,000, and (C) either or both of sulfonium salt compounds represented by the following general formulae (1-1) and (1-2). There can be provided a conductive polymer material that has low acidity, can suppress the gradual agglomeration of particles, and has excellent solution-stability.

First claim

What is claimed is:

1. A conductive polymer material comprising:
(A) a π-conjugated polymer;
(B) a dopant polymer which contains a repeating unit having a sulfo group and has a weight-average molecular weight in the range of 1,000 to 500,000; and
(C) either or both of sulfonium salt compounds represented by the following general formulae (1-1) and (1-2),

wherein R 1 , R 2 , and R 3 independently represent a halogen atom, an amino group that contains an alkyl group having 1 to 4 carbon atoms, a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, in which these groups may contain an alkoxy group, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an amino group, a halogen atom, an ester group, an ether group, or a thioether group; R 1 and R 2 may form a ring together with each other, and when the ring is formed, R 1 and R 2 represent an alkylene group having 1 to 6 carbon atoms; R 4 , R 5 , and R 6 independently represent an alkyl group having 1 to 4 carbon atoms; K − is selected from the group consisting of a hydroxide ion, a chloride ion, a bromide ion, a carbonate ion, a hydrogen carbonate ion, a nitrate ion, a carboxylate ion, a sulfonate ion, and a sulfinate ion; and when K − is a carboxylate ion, K − is optionally substituted for any of R 1 , R 2 , and R 3 to form an inner salt.

2. The conductive polymer material according to claim 1 , wherein the component (B) has a sulfo group whose a-position is fluorinated and/or a sulfo group bonded to a fluorinated aromatic group.

3. The conductive polymer material according to claim 2 , wherein the component (B) contains one or more repeating units selected from (2-1) to (2-4) represented by the following general formula (2),

wherein R 7 , R 9 , R 12 , and R 14 each represent a hydrogen atom or a methyl group; R 8 , R 10 , and R 13 each represent a single bond, an ester group, or a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms and optionally having either or both of an ether group and an ester group; R 11 represents a linear or branched alkylene group having 1 to 4 carbon atoms, in which 1 or 2 hydrogen atoms in R 11 is optionally substituted with a fluorine atom; R 15 represents a fluorine atom or a trifluoromethyl group; Z 1 and Z 2 each represent a phenylene group, a naphthylene group, or an ester group; Z 3 represents a single bond, a phenylene group, a naphthylene group, an ether group, or an ester group; Z 4 represents a single bond or an ester group; provided that when Z 2 is a phenylene group, R 10 does not contain an ether group; “p” is an integer of 1 to 4; and “a1”, “a2”, “a3”, and “a4” are each a number satisfying 0≦a1≦1.0, 0≦a2≦1.0, and 0≦a3≦1.0, 0≦a4≦1.0, and 0<a1+a2+a3+a4≦1.0.

4. The conductive polymer material according to claim 3 , wherein the component (B) contains a repeating unit represented by the following general formula (3),

wherein “b” is a number satisfying 0<b≦1.0.

5. The conductive polymer material according to claim 3 , wherein the component (B) is a block copolymer.

6. The conductive polymer material according to claim 3 , wherein the component (A) is a polymer formed by polymerization of one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclic aromatic compound, and a derivative thereof.

7. The conductive polymer material according to claim 2 , wherein the component (B) contains a repeating unit represented by the following general formula (3),

wherein “b” is a number satisfying 0<b≦1.0.

8. The conductive polymer material according to claim 2 , wherein the component (B) is a block copolymer.

9. The conductive polymer material according to claim 2 , wherein the component (A) is a polymer formed by polymerization of one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclic aromatic compound, and a derivative thereof.

10. The conductive polymer material according to claim 1 , wherein the component (B) contains one or more repeating units selected from (2-1) to (2-4) represented by the following general formula (2),

wherein R 7 , R 9 , R 12 , and R 14 each represent a hydrogen atom or a methyl group; R 8 , R 10 , and R 13 each represent a single bond, an ester group, or a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms and optionally having either or both of an ether group and an ester group; R 11 represents a linear or branched alkylene group having 1 to 4 carbon atoms, in which 1 or 2 hydrogen atoms in R 11 is optionally substituted with a fluorine atom; R 15 represents a fluorine atom or a trifluoromethyl group; Z 1 and Z 2 each represent a phenylene group, a naphthylene group, or an ester group; Z 3 represents a single bond, a phenylene group, a naphthylene group, an ether group, or an ester group; Z 4 represents a single bond or an ester group; provided that when Z 2 is a phenylene group, R 10 does not contain an ether group; “p” is an integer of 1 to 4; and “a1”, “a2”, “a3”, and “a4” are each a number satisfying 0≦a1≦1.0, 0≦a2≦1.0, and 0≦a3≦1.0, 0≦a4≦1.0, and 0<a1+a2+a3+a4≦1.0.

11. The conductive polymer material according to claim 10 , wherein the component (B) contains a repeating unit represented by the following general formula (3),

wherein “b” is a number satisfying 0<b≦1.0.

12. The conductive polymer material according to claim 10 , wherein the component (B) is a block copolymer.

13. The conductive polymer material according to claim 10 , wherein the component (A) is a polymer formed by polymerization of one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclic aromatic compound, and a derivative thereof.

14. The conductive polymer material according to claim 1 , wherein the component (B) contains a repeating unit represented by the following general formula (3),

wherein “b” is a number satisfying 0<b≦1.0.

15. The conductive polymer material according to claim 1 , wherein the component (B) is a block copolymer.

16. The conductive polymer material according to claim 1 , wherein the component (A) is a polymer formed by polymerization of one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurophene, aniline, a polycyclic aromatic compound, and a derivative thereof.

17. The conductive polymer material according to claim 1 , wherein the conductive polymer material has dispersibility in water or in an organic solvent.

18. A substrate having a conductive film formed th

Assignees

• Shinetsu Chemical Co

Inventors

• Hatakeyama Jun
• Nagasawa Takayuki

Classifications

• H01B1/124

  Intrinsically conductive polymers · CPC title

• H01B1/127

  comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes · CPC title

• H01B1/128 Primary

  comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes · CPC title