Polymerization liquid, conductive polymer film obtained from polymerization liquid, and solid electrolytic capacitor
Provided is a polymerization liquid for electropolymerization, which uses a solvent that is mainly composed of water, which is greatly increased in the amount of a monomer contained therein, and which is capable of quickly forming a conductive polymer layer having high conductivity and heat resistance, A polymerization liquid for electropolymerization of the present invention contains: a solvent that is composed of 100-80% by mass of water and 0-20% by mass of an organic solvent; at least one monomer having a pi-conjugated double bond; at least one supporting electrolyte; and at least two nonionic surfactants. The at least two nonionic surfactants are composed of at least one acetylenol surfactant and at least one water-soluble nonionic surfactant other than the acetylenol surfactant. Due to the combination of the two nonionic surfactants, the amount of the monomer emulsified with the solvent can be greatly increased.
1. A polymerization liquid for electrolytic polymerization of at least one monomer with a π-conjugated double bond, comprising:
a solvent composed of 100 to 80% by mass of water and 0 to 20% by mass of an organic solvent;
at least one supporting electrolyte;
a composite nonionic surfactant composed of:
at least one acetylenol surfactant of the formula (1):
where a is 0 or 1,
b is an integer number of 0, 1 or more than 1,
c is an integer number of 0, 1 or more than 1,
d is an integer number of 0, 1 or more than 1, and
e is an integer number of 0, 1 or more than 1,
provided that 0≦b+e≦100 and 0≦c+d≦100;
R 1 is hydrogen or methyl group,
R 2 , R 3 and R 4 may be the same or different and are independently linear or branched alkyl or alkenyl groups having 1 to 8 carbon atoms,
R 5 is a linear or branched alkylene or alkenylene group having 1 to 4 carbon atoms, and
R 6 is hydrogen, methyl or ethyl group; and
at least one water-soluble nonionic surfactant other than the acetylenol surfactant; and
the monomer emulsified with the solvent by the composite nonionic surfactant.
2. The polymerization liquid according to claim 1 , wherein a in the formula (I) is 0.
3. The polymerization liquid according to claim 2 , wherein the acetylenol surfactant of the formula (I) is 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
4. The polymerization liquid according to claim 1 , wherein the water-soluble nonionic surfactant other than the acetylenol nonionic surfactant is at least one compound selected from a group consisting of polyoxyethylene alkylphenyl ethers.
5. The polymerization liquid according to claim 3 , wherein the water-soluble nonionic surfactant other than the acetylenol nonionic surfactant is at least one compound selected from a group consisting of polyoxyethylene alkylphenyl ethers.
6. The polymerization liquid according to claim 1 , wherein the solvent consists of water only.
7. The polymerization liquid according to claim 1 , wherein the monomer is at least one compound selected from a group consisting of 3,4-disubstituted thiophenes.
8. The polymerization liquid according to claim 5 , wherein the monomer is at least one compound selected from a group consisting of 3,4-disubstituted thiophenes.
9. The polymerization liquid according to claim 1 , wherein the supporting electrolyte is at least one compound selected from a group consisting of organic non-sulfonate supporting electrolytes having an anion with the molecular weight of 200 or more.
10. The polymerization liquid according to claim 9 , wherein the supporting electrolyte is at least one compound selected from a group consisting of borodisalicylic acid and borodisalicylic salts.
11. The polymerization liquid according to claim 10 , further comprising at least one stabilizer selected from a group consisting of nitrobenzene and nitrobenzene derivatives.
12. The polymerization liquid according to claim 8 , wherein the supporting electrolyte is at least one compound selected from a group consisting of borodisalicylic acid and borodisalicylic salts.
13. The polymerization liquid according to claim 12 , further comprising at least one stabilizer selected from a group consisting of nitrobenzene and nitrobenzene derivatives.
14. A conductive polymer film obtained by introducing a substrate with a conductive part at least on the surface into the polymerization liquid according to claim 1 and performing electrolytic polymerization.
15. A solid electrolytic capacitor comprising: a positive electrode composed of a valve metal foil with an oxide film on the surface; and a conductive polymer layer located on the positive electrode, wherein the conductive polymer layer is formed by introducing the positive electrode into the polymerization liquid according to claim 1 and performing electrolytic polymerization.
16. A solid electrolytic capacitor comprising: a positive electrode composed of a valve metal foil with an oxide film on the surface; a negative electrode composed of a valve metal foil; and a separator having a conductive polymer layer between the positive electrode and the negative electrode, wherein the conductive polymer layer is formed by introducing a capacitor element with the positive electrode, the negative electrode, and a separator between the positive electrode and the negative electrode into a polymerization liquid according to claim 1 , thereby immersing the polymerization liquid into the capacitor element, and performing electrolytic polymerization.
17. A solid electrolytic capacitor comprising: a positive electrode composed of a valve metal foil with an oxide film on the surface; and a conductive polymer layer located on the positive electrode, wherein the conductive polymer layer is formed by introducing the positive electrode into the polymerization liquid according to claim 8 and performing electrolytic polymerization.
18. A solid electrolytic capacitor comprising: a positive electrode composed of a valve metal foil with an oxide film on the surface; a negative electrode composed of a valve metal foil; and a separator having a conductive polymer layer between the positive electrode and the negative electrode, wherein the conductive polymer layer is formed by introducing a capacitor element with the positive electrode, the negative electrode, and a separator between the positive electrode and the negative electrode into a polymerization liquid according to claim 8 , thereby immersing the polymerization liquid into the capacitor element, and performing electrolytic polymerization.
19. A solid electrolytic capacitor comprising: a positive electrode composed of a valve metal foil with an oxide film on the surface; and a conductive polymer layer located on the positive electrode, wherein the conductive polymer layer is formed by introducing the positive electrode into the polymerization liquid according to claim 13 and performing electrolytic polymerization.
20. A solid electrolytic capacitor comprising: a positive electrode composed of a valve metal foil with an oxide film on the surface; a negative electrode composed of a valve metal foil; and a separator having a conductive polymer layer between the positive electrode and the negative electrode, wherein the conductive polymer layer is formed by introducing a capacitor element with the positive electrode, the negative electrode, and a separator between the positive electrode and the negative electrode into a polymerization liquid according to claim 13 , thereby immersing the polymerization liquid into the capacitor element, and performing electrolytic polymerization.