JP2009270011A - Conjugated polymer compound with controlled electron state and organic semiconductor material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conjugated polymer compound in which electron state is controlled. <P>SOLUTION: An electron state of the conjugated polymer compound represented by general formula (I) is controlled by introducing a cyano group as an electron acceptor into a side chain. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conjugated polymer compound having conductivity by π conjugation in an organic polymer main chain. The present invention also relates to a method for controlling the electronic state of a conjugated polymer compound and a method for producing the conjugated polymer compound. Furthermore, the present invention relates to a conductive polymer material having an absorption wavelength in the sunlight region, which is used for a p-type organic semiconductor of an organic thin film solar cell.

  The organic thin film solar cell has a simple element structure in which a p-type (electron donor property) organic semiconductor and an n-type (electron acceptor property) organic semiconductor are combined, and is a wet solar cell represented by dye-sensitized solar electrons. In contrast, since no electrolytic solution is used, it is excellent in workability and can be formed into a desired shape. Moreover, since it can be made much lighter than a silicon solar cell or a dye-sensitized solar cell, it can also be used for the roof of a huge building. Furthermore, since there are no resource restrictions like high-purity silicon and precious metals, it is a next-generation solar cell that is estimated to be able to greatly reduce costs as the market share expands.

The problem is to improve the energy conversion efficiency, and the current maximum value is about 4 to 5% for a single junction, and 6.5% for an improved multi-junction. As can be seen from this result, there is a limit to the optimization of the element structure in order to improve the practical line of thin-film solar cells to 12 to 15%, and a breakthrough is necessary to optimize the materials used. It is.

Through a series of organic thin-film solar cell researches that are underway around the world, fullerene derivatives (PCBM) have been found to be optimal as n-type semiconductors. It is known that HOMO (maximum occupied molecular orbital) of PCBM is 6.0 eV and LUMO (lowest unoccupied molecular orbital) is 4.2 eV. It has been proposed that the LUMO of the corresponding p-type semiconductor is preferably 0.3 eV higher than the LUMO of PCBM (Non-Patent Document 1). This is because an energy difference of at least 0.3 eV is required for effective charge separation. If the energy difference is larger than that, it is not desirable because the excitation energy for absorbing light is wasted.
Furthermore, the band gap (difference between LUMO level and HOMO level) of the conjugated polymer (p-type semiconductor) is required to be about 1.5 eV in consideration of efficient absorption of sunlight. When the band gap is small, light absorption occurs in a wide wavelength range, so that the short circuit current density increases, but the open circuit voltage decreases. Conversely, when the band gap is large, the open circuit voltage increases, but the short-circuit current density decreases because of less light absorption. Considering the balance between the two, the maximum efficiency is around the band gap of 1.5 eV.

Currently, the most commonly used p-type semiconductor polymers are conjugated polymer compounds such as polythiophene derivatives and polyphenylene vinylene derivatives. Although these HOMO levels are close to ideal values, the LUMO levels are significantly higher. High is a problem. The HOMO level can be adjusted relatively easily by introducing a thiophene ring or an electron-rich conjugated electron system (such as an aromatic amino group) (Non-patent Document 2).
On the other hand, in order to lower the LUMO level, it is necessary to introduce an electron acceptor site, and the main conventional approach is alternating copolymerization of a donor and an acceptor. However, in this method, it is necessary to perform a complicated polymerization operation every time in order to create different electronic states, and it was almost impossible to create a comprehensive electronic state library.

By the way, the present inventor previously described an electron-donating group for the following reaction in which a tetracyanobutadiene skeleton is formed by a ring-opening reaction followed by [2 + 2] cycloaddition of an electron-rich alkyne and a strong acceptor molecule, tetracyanoethylene. It was discovered that the reaction proceeds almost quantitatively at room temperature when an aromatic amino group is used (Non-patent Document 3).

(In the above reaction formula, R represents an arbitrary substituent, and EDG represents an electron donating group.)
And it discovered that reactivity increased when the phenyl group which has an amine in a para position or an ortho position was used among the aromatic amino groups used as an electron-donating group (nonpatent literature 4).
This reaction is a one-step reaction that can quantitatively give the target compound under mild conditions, and can be called a “click-type reaction”.

However, it was not clear whether the above click-type reaction could be applied to a conjugated polymer.
Recently, a one-step alternating addition reaction of tetracyanoethylene and tetrathiafulvalene to a polyyne structure has been reported (Non-patent Document 5), which is an application to oligomers or oligodendrimers, It was not clear whether it could be applied to conductive polymers. Moreover, although addition reaction of tetracyanoethylene to acetylene having a ferrocene group at room temperature has been reported (Non-patent Document 6), this is also a reaction with a monomer, and a linear conductive polymer. It was not clear whether it could be applied.

Barry C. Thompson et al., January 2008, Angelwandte Chemie International Edition, Vol. 47, Issue 1, pp. 58-77 Tsuyoshi Michinobu and 2 others, 2007, Chemistry Letters, Vol.36, No.5, pp.620-621 Tsuyoshi Michinobu and 8 others, 2005, Chemical Communications, Issue 6, pp.737-739 Tsuyoshi Michinobu and 7 others, 2006, Chemistry A European Journal, Vol. 12, Issue 7, pp.1889-1905 Milan Kivala and 5 others, 2007, Angelwandte Chemie International Edition, Vol.46, Issue 33, pp.6357-6360 Tomoyuki Mochida and 1 other, 2002, Dalton Transactions, Issue 18, pp.3559-3564

  In view of the above-described conventional situation, the present invention provides a conjugated polymer compound having a desired electronic state by controlling an electronic state such as a LUMO level of a conjugated polymer compound used for a p-type semiconductor or the like of an organic thin film solar cell. The purpose is to develop a method for easily obtaining the above.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, as shown in the following reaction formula (1), a conjugated polymer compound having an ethynylene group (carbon-carbon triple bond) in the side chain has It has been found that an electron acceptor group can be easily added to a conjugated polymer compound by adding a strong acceptor molecule having a cyanoethylene structure. In addition, by adjusting the amount of molecules added, the amount of cyano groups introduced as electron acceptors can be controlled, and the electronic state of the conjugated polymer compound can be widely controlled, completing the present invention. It came to do.

  That is, the present invention provides the following conjugated polymer compounds with controlled electronic states (1) to (12) and (18), and conjugated polymers with controlled electronic states (13) to (17) below. A method for producing a compound, a p-type conductive polymer material for an organic thin film solar cell of (19) below, an organic thin film solar cell element of (20) below, and an organic thin film solar cell of (21) below are provided. .

:
A conjugated polymer compound represented by the following general formula (I):

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

(2):
In the conjugated polymer compound described in (1) above, at least one of R ₁ and R ₂ may have a phenyl group having an amine or a substituent in at least one of the para position and the ortho position, or a ferrocene-containing group. A conjugated polymer compound characterized by being an electron donating group of

(3):
The conjugated polymer compound according to (2), wherein at least one of R ₁ and R ₂ is a phenyl group having an amine in at least one of a para position and an ortho position.

(4):
In the conjugated polymer compound according to (3), R ₂ is a phenyl group having an amine at the para position, and the conjugated polymer compound represented by the following general formula (II):

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond, or an electron donating group. R ₃ and R ₄ represent a group having a π bond or a single bond, and at least of R ₃ and R ₄ One represents a group having a π bond, R ₅ represents an aryl group having a quinoid structure or a double bond, and R ₆ represents one or more monomer structural units each composed of a group having a π bond. X, y, and z are natural numbers that satisfy the following expressions: 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100, and x + y + z = 100, respectively, (Shows the numerical value shown.)

(5):
The conjugated polymer compound as described in (4) above, wherein R ₁ is a group having a π bond or an electron donating group.

(6):
In the conjugated polymer compound described in (5), R ₃ is a single bond, R ₄ is a group having a π bond, R ₅ is a double bond, and z is 0. A conjugated polymer compound represented by the following general formula (III):

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X and y are 0 ≦ x <100, 0 <y ≦, respectively. (It is a natural number satisfying the equation of 100 and x + y = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

(7):
In the conjugated polymer compound described in (2), R ₁ is a phenyl group having an amine in at least _one of a para position and an ortho position, and R ₂ is a group having a π bond. Conjugated polymer compounds.

(8):
The conjugated polymer compound according to (1), wherein R ₆ is two types of monomer constituent units composed of a group having a π bond, and is represented by the following general formula (IV):

(In the formula, R ₁ and R ₁ ′ represent a hydrogen atom, a group having a π bond, or an electron donating group. R ₂ and R ₂ ′ represent an electron donating group or a group having a π bond, and R ₃ , R ₃ ′, R ₄ , and R ₄ ′ represent a group having a π bond or a single bond (provided that at least one of R ₁ and R ₂ represents an electron-donating group, and R ₁ ′ and R ₂ And at least one of ′ represents an electron donating group. At least one of R ₂ , R ₃ and R ₄ represents a group having a π bond, and at least one of R ₂ ′, R ₃ ′ and R ₄ ′. One represents a group having a π bond) R ₅ and R ₅ ′ represent an aryl group having a quinoid structure or a double bond, and x, y, z ₁ and z ₂ are each 0 ≦ x < l00, 0 <y ≦ 100, 0 ≦ z ₁ <100, 0 <z ₂ <100 and x + y + z ₁ + z ₂ = 10 (It is a natural number satisfying the equation of 0, and represents a numerical value indicating the polymerization ratio of the monomer.)

(9):
An electron-donating group is a phenyl group having an amine in at least one of the para-position and the ortho-position, a phenyl group having an alkoxy group in at least one of the para-position and the ortho-position, an amino group, a mono-substituted amino group, a di-substituted amino group, A ferrocene-containing group which may have a substituent, a thiophene-containing group which may have a substituent, a pyrrole-containing group which may have a substituent, and a carbazole which may have a substituent The conjugated polymer compound according to any one of (1) to (6) and (8) above, which is an electron donating group selected from the group consisting of groups.

(10):
The conjugated polymer compound as described in (9) above, wherein the electron donating group is a phenyl group having an amine at the para or ortho position.

(11):
A group having a π bond is thiophene, phenylene, phenylene vinylene, fluorene, phenylene ethynylene, vinylene, ethynylene, thiazole, benzodithiophene, thienothiophene, dithienothiophene, cyclopentadithiophene, triphenylamine, pyrrole, 2, Any one of (1) to (10) above, which is a group containing one or more chemical structures selected from the group consisting of 1,3-benzothiadiazole, thienopyrazine and 1H-benzo [de] anthracene The conjugated polymer compound described in 1.

(12):
The aryl group having a quinoid structure is a cyclohexa-2,5-diene-1,4-diylidene group, 2,3,5,6-tetrafluorohexa-2,5-diene-1,4-diylidene group, naphthalene Any of the above (1) to (5) and (7) to (11), which is a group selected from the group consisting of a -2,6-diylidene group and an anthracene-9,10-diylidene group A conjugated polymer compound as described above.

(13):
The following reaction to obtain the conjugated polymer compound represented by the following general formula (I) by reacting the conjugated polymer compound represented by the following general formula (V) with the compound represented by the following general formula (VI) The manufacturing method of the conjugated polymer compound as described in said (1) characterized by including the process shown by Formula (1).

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

(14):
A conjugated polymer compound represented by the following general formula (III) is reacted with a tetracyanoethylene represented by the following general formula (A-1) to the conjugated polymer compound represented by the following general formula (VII). The method for producing a conjugated polymer compound according to (6) above, which comprises the step shown in the following reaction formula (2) to obtain:

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X and y are 0 ≦ x <100, 0 <y, respectively. ≦ 100 and x + y = 100 are natural numbers that satisfy the formulas and represent numerical values indicating the polymerization ratio of monomers.)

(15):
In the production method according to the above (14), the compound represented by the following general formula (VIII) is further reacted with the compound represented by the following general formula (IX) to obtain a compound represented by the following general formula (VII). A process for producing a conjugated polymer compound comprising a step represented by the following reaction formula (3) for synthesizing a conjugated polymer compound:

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X represents a halogen atom. X + y represents a monomer polymerized. (Indicates that it is a polymer.)

(16):
The manufacturing method of the conjugated polymer compound characterized by including the process of following (A)-(C):
(A) By changing the abundance ratio of the conjugated polymer compound represented by the following general formula (V) and the compound represented by the following general formula (VI), a plurality of reactions represented by the following reaction formula (1) are performed. Process;
(B) Measurement of electronic state of a plurality of conjugated polymer compounds obtained by the step (A) represented by the following general formula (I) and having different ratios of x and y Performing the steps;
(C) A step of selecting a conjugated polymer compound having a desired electronic state.

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

(17):
In the step (C), a conjugated polymer compound having a HOMO level of 5.2 to 5.6 eV and a LUMO level of 3.7 to 4.1 eV is selected. The manufacturing method of the conjugated polymer compound as described in 16).

(18):
A conjugated polymer compound obtained by the production method according to any one of (16) and (17).

(19):
The p-type conductive polymer material for organic thin-film solar cells containing the conjugated polymer compound in any one of said 1-12 and 18.

(20):
An organic thin-film solar cell element comprising a first electrode layer, a photoelectric conversion layer containing the p-type conductive polymer material described in (19), and a second electrode layer.

(21):
One or more organic thin-film solar cell elements described in said (20) are included, The organic thin-film solar cell characterized by the above-mentioned.

  In the conjugated polymer compound of the present invention and the method for producing the conjugated polymer compound, the introduction amount of the cyano group serving as an electron acceptor into the conjugated polymer can be controlled by adjusting the amount of the strong acceptor molecule to be added. It is possible to easily provide a comprehensive library of conjugated polymer compounds having an electronic state.

  By using the conjugated polymer compound of the present invention, it becomes possible to select a conjugated polymer compound having an ideal electronic state from an exhaustive library of conjugated polymer compounds having various electronic states. It is possible to strongly promote the practical application of organic thin-film solar cells, which are next-generation solar cells.

  Moreover, since the conjugated polymer compound of the present invention exhibits a visible light absorption effect derived from a donor-acceptor interaction between an electron donor in a molecule and a cyano group (electron acceptor), an excellent photoelectric effect can be expected. Is.

  Furthermore, since the conjugated polymer compound of the present invention adds an electron acceptor to the side chain, the addition reaction is easier than when an electron acceptor is added to the main chain. In addition, when the main chain has alternating donors and acceptors, the donor-acceptor interaction only works between adjacent groups, whereas the entire main chain is a donor (acceptor) and the side chain has an acceptor (donor). In the conjugated polymer compound of the present invention, the donor-acceptor interaction can be synergistically enhanced.

  The conjugated polymer compound represented by the general formula (II) of the present invention can be produced at room temperature, without a by-product in a one-step reaction, in an extremely high yield, and without using a catalyst. This is an excellent effect.

Hereinafter, the best mode for carrying out the present invention will be described. The present invention is not limited to the following embodiment.
In the conjugated polymer compound of the present invention, as shown in the following reaction formula (1), the compound represented by the general formula (VI) is added to the compound represented by the general formula (V), and both are reacted. Can be manufactured.

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

  The addition reaction to alkyne in the present invention is considered to be due to the following reaction mechanism.

(In the above reaction mechanism, R represents an arbitrary substituent, and EDG represents an electron donating group.)

  In the above reaction formula (1), by performing a plurality of reactions in which the amount of the compound represented by the general formula (VI) added to the conjugated polymer compound represented by the general formula (V) is appropriately changed, A plurality of conjugated polymer compounds having different ratios of x and y in formula (I) can be obtained. By increasing the amount of the compound represented by the general formula (VI), the value of y increases. Therefore, a plurality of reactions in which the amount of the compound represented by the general formula (VI) is increased from 0 by a certain amount are performed. If it carries out, the compound library which the ratio of x and y increased little by little can be created. And by increasing the value of y, it can be expected that the LUMO value of the conjugated polymer compound is greatly reduced and the HOMO value is reduced to a small value. Therefore, by measuring the electronic state of the conjugated polymer compound in the library, A conjugated polymer compound having values close to the desired LUMO value and HOMO value can be selected from the library.

That is, this invention provides the manufacturing method of the conjugated polymer compound characterized by including the process of following (A)-(C):
(A) A step of performing a plurality of reactions represented by the reaction formula (1) by changing the abundance ratio of the conjugated polymer compound represented by the general formula (V) and the compound represented by the general formula (VI);
(B) The electronic state of a plurality of conjugated polymer compounds represented by the general formula (I) obtained by the step (A) and having different ratios of x and y is measured. Process;
(C) A step of selecting a conjugated polymer compound having a desired electronic state.

Here, the method for measuring the electronic state of the conjugated polymer compound is not particularly limited, and for example, an electrochemical measurement method and an absorption / emission spectrum measurement method can be used.
First, the HOMO level can be determined by setting the oxidized electrons obtained by cyclic voltammetry measurement in dichloromethane to a relative potential of Fc / Fc ⁺ (4.8 eV).
Next, ultraviolet, visible, and near infrared absorption spectra are measured in dichloromethane. The visible (and near-infrared) absorption terminal energy is obtained while maintaining consistency with the emission wavelength, and is set as an optically calculated band gap value. The LUMO level can be calculated from the HOMO level determined by the electrochemical measurement method and the band gap value determined by the absorption / emission spectrum measurement method.

  In the step (C), when a conjugated polymer compound having a HOMO level of 5.2 to 5.6 eV and a LUMO level of 3.7 to 4.1 eV is selected, the organic thin film solar cell has n When the type semiconductor is a fullerene derivative (PCBM), a conjugated polymer compound close to the ideal electronic state (HOMO level = 5.4 eV, LUMO level = 3.9 eV) of the p-type semiconductor can be obtained.

In the reaction formula (1), when either R ₁ or R ₂ adjacent to the ethynylene group (carbon-carbon triple bond) of the conjugated polymer compound represented by the general formula (V) is an electron donating group The reactivity of the reaction for adding the compound represented by the general formula (VI) is enhanced.

Here, examples of the electron donating group include a phenyl group having an amine in at least one of the para-position and the ortho-position, a phenyl group having an alkoxy group in at least one of the para-position and the ortho-position, an amino group, a mono-substituted amino group, A substituted amino group, a ferrocene-containing group that may have a substituent, a thiophene-containing group that may have a substituent, a pyrrole-containing group that may have a substituent, or a substituent. Any of the other carbazole-containing groups may be used.

Here, the substituent is not particularly limited as long as the group is not so reactive. For example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, an alkoxy group Group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, An alkylsulfonyl group, an arylsulfonyl group, an amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a silyl group, and the like can be used.

Since either _one of R ₁ and R ₂ is an electron donating group, the reactivity of the above reaction formula (1) is enhanced, and thus the production method of the present invention is performed under conditions of, for example, 0 to 300 ° C. Below, it can carry out in an organic solvent without a catalyst or using catalysts, such as a transition metal.

In a preferred embodiment of the present invention, in the conjugated polymer compound represented by the general formula (V) in the reaction formula (1), at least one of R ₁ and R ₂ adjacent to the ethynylene group (carbon-carbon triple bond) is used. A certain electron-donating group is a phenyl group having an amine in at least one of the para-position and the ortho-position or a ferrocene-containing group optionally having a substituent. In this case, the reactivity is further increased. be able to.
In a more preferred embodiment of the present invention, in the conjugated polymer compound represented by the general formula (V) in the reaction formula (1), the electron donating group in at least one of R ₁ and R ₂ is substituted with the para position and the ortho group. The phenyl group having an amine in at least one of the positions.

A conjugated polymer compound in which at least one of R ₁ and R ₂ in the general formula (V) is a phenyl group having an amine in at least one of the para position and the ortho position or a ferrocene-containing group optionally having a substituent Examples of the conjugated polymer compound include, but are not limited to, conjugated polymer compounds represented by the following general formulas (X) to (XVI).

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond, or an electron donating group. R ₂ represents a group having an π bond or an electron donating group, and R ₃ and R ₄ represent a π bond. (Wherein any one of R ₂ , R ₃ and R ₄ represents a group having a π bond) R ₆ is one or more of groups having a π bond R and R ′ each represent a hydrogen atom, an alkyl group or an aryl group, and x, y and z are 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and (It is a natural number satisfying the formula x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

  Among these, it is particularly preferable to use a compound represented by the general formula (X). A compound represented by the following general formula (VI) is added to the compound represented by the general formula (X) to obtain a conjugated polymer compound represented by the following general formula (II). The production method represented by the formula (4) has an excellent effect that it can be produced at room temperature, without a by-product in a one-step reaction, in an extremely high yield, and without using a catalyst. Is.

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond, or an electron donating group. R ₃ and R ₄ represent a group having a π bond or a single bond, and at least of R ₃ and R ₄ One represents a group having a π bond, R ₅ represents an aryl group having a quinoid structure or a double bond, and R ₆ represents one or more monomer structural units each composed of a group having a π bond. X, y, and z are natural numbers that satisfy the following expressions: 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100, and x + y + z = 100, respectively, (Shows the numerical value shown.)

  Examples of the solvent used in the reaction formula (4) include, but are not limited to, dichloroethane, THF (tetrahydrofuran), dichloromethane, chloroform, chlorobenzene, dichlorobenzene, benzene, toluene, acetonitrile, and the like. be able to.

In the case where R ₁ is a hydrogen atom, the conjugated polymer compound represented by the general formula (II) obtained by the above reaction formula (4) has a chemical structure as demonstrated in Example 3 of the present specification. A polymer compound with reduced stability is obtained. In the case of a low molecular weight compound having a similar structure, since the chemical stability is high, this is a phenomenon peculiar to a polymer and cannot be predicted at all from the prior art.
That is, the present invention provides a conjugated polymer compound having high chemical stability in which R ₁ is a group having a π bond or an electron donating group in the compound represented by the general formula (II). .

  In the above reaction formulas (1) and (4), a strong acceptor molecule represented by the following general formula (VI) is used.

(In the formula, R ₅ represents an aryl group having a quinoid structure or a double bond.)

Here, the aryl group having a quinoid structure is not particularly limited, and examples thereof include a cyclohexa-2,5-diene-1,4-diylidene group, 2,3,5,6-tetrafluorohexa-2,5. -Diene-1,4-diylidene group, naphthalene-2,6-diylidene group, anthracene-9,10-diylidene group, phenanthrene-3,9-diylidene group, phenanthrene-2,7-diylidene group and the like.
Among these, cyclohexa-2,5-diene-1,4-diylidene group, 2,3,5,6-tetrafluorohexa-2,5-diene-1,4-diylidene group, naphthalene-2,6 -Diylidene group and anthracene-9,10-diylidene group are preferable.

Examples of the compound represented by the general formula (VI) include, but are not limited to, compounds represented by the following structural formulas (A-1) to (A-5).

In the general formula (VI), when R ₅ is a double bond, tetracyanoethylene represented by the structural formula (A-1) is obtained.
In the general formula (VI), when R ₅ is a cyclohexa-2,5-diene-1,4-diylidene group, tetracyanoquinodimethane represented by the structural formula (A-2) is obtained.
In the general formula (VI), when R ₅ is 2,3,5,6-tetrafluorohexa-2,5diene-1,4-diylidene group, the tetra represented by the structural formula (A-3) is used. It becomes fluorotetracyanoquinodimethane.
In the general formula (VI), when R ₅ is a naphthalene-2,6-diylidene group, 11,11,12,12-tetracyanonaphtho-2,6- It becomes quinodimethane.
In the general formula (VI), when R ₅ is an anthracene-9,10-diylidene group, 9,10-bis (dicyanomethylene) -9,10-dihydroanthracene represented by the above structural formula (A-5) It becomes.

As the compound represented by the general formula (VI), it is most preferable to use tetracyanoethylene represented by the structural formula (A-1).
If tetracyanoethylene is used, a side reaction is not induced even if it is added in excess, so that tetracyanoethylene can be easily removed by sublimation purification, and the production cost can be reduced. Moreover, if the weight increase is calculated from the weight of the reaction product after removing tetracyanoethylene by sublimation purification, the reaction yield can be easily calculated.

  In the present invention, the conjugated polymer compound has a main chain in which a double bond or a triple bond containing carbon-carbon or a hetero atom is connected via a single bond or a hetero atom, and is made conductive by a π-conjugated system. It means an organic polymer compound having.

In the conjugated polymer compound represented by the following general formula (I) of the present invention, the main chain composed of R ₂ , R ₃ , R ₄ and R ₆ has a double bond or triple bond containing carbon-carbon or a hetero atom. Any structure may be used as long as it has a structure in which the bond is connected through a single bond or a hetero atom and has conductivity by a π-conjugated system.

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

  Here, the group having a π bond is not particularly limited as long as it is a group capable of forming a π conjugated system in the main chain, and examples thereof include thiophene, phenylene, phenylene vinylene, fluorene, phenylene ethynylene, vinylene, ethynylene, thiazole, Benzodithiophene, thienothiophene, dithienothiophene, cyclopentadithiophene, triphenylamine, pyrrole, 2,1,3-benzothiadiazole, thienopyrazine, 1H-benzo [de] anthracene, pentalene, indene, naphthalene, azulene, heptalene , Biphenylene, acenaphthylene, phenalene, phenanthrene, anthracene, fluoranthene, acephananthrylene, acanthrylene, triphenylene, pyrene, chrysene, naphthacene, preaden, picene, perylene, pen N-taphene, pentacene, hexaphene, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyrantolene, obalene, furan, pyridine, oxazole, thiazole, imidazole, pyrazole, pyrazine, pyrimidine, benzofuran, benzothiophene, indole, carbazole, quinoline, fe It is a group comprising one or more chemical structures selected from the group consisting of nanthridine, acridine, benzimidazole, quinoxaline, quinazoline, purine, pteridine, phenanthroline, thianthrene and phenazine.

  Here, the “group including one or more chemical structures” is a divalent or trivalent group including a chemical structure selected from the group listed above, or a group having a substituent added to the group. Or two or more of the chemical structures selected from the groups listed above are a divalent or trivalent group linked via a single bond or a heteroatom, or a substituent is added to the group Means a group.

Preferred groups having a π bond are thiophene, phenylene, phenylene vinylene, fluorene, phenylene ethynylene, vinylene, ethynylene, thiazole, benzodithiophene, thienothiophene, dithienothiophene, cyclopentadithiophene, triphenylamine, pyrrole , 2,1,3-benzothiadiazole, thienopyrazine and 1H-benzo [de] anthracene.

  Examples of the group having a π bond include, but are not limited to, groups represented by the following general formulas (B-1) to (B-14).

(In the formula, each R is independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, Group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, A halogen atom, a fluorinated hydrocarbon group, a cyano group, a silyl group, etc., and two Rs may form a ring, and when these groups having a π bond are R ₂ , The ethynylene group (carbon-carbon triple bond) that becomes the side chain of the conjugated polymer compound of the invention (It may be linked to R.)

In the general formulas (I), (II), (V), and (X) to (XVI), R ₆ represents one or more monomer structural units composed of a group having a π bond. . That is, in the conjugated polymer compound of the present invention, in addition to a monomer having a side chain in which an addition reaction occurs, one or more other monomers may be copolymerized. Moreover, the said other monomer is not copolymerized and z may be 0 in the said general formula (I), (II), (V) and (X)-(XV).
R ₆ may be a monomer having an ethynylene group (carbon-carbon triple bond) in the side chain. In this case, the compound represented by the general formula (VI) is also added to the side chain of R _6. Therefore, the conjugated polymer compound represented by the general formula (I) becomes a conjugated polymer compound represented by the following general formula (IV).

(In the formula, R ₁ and R ₁ ′ represent a hydrogen atom, a group having a π bond, or an electron donating group. R ₂ and R ₂ ′ represent an electron donating group or a group having a π bond, and R ₃ , R ₃ ′, R ₄ , and R ₄ ′ represent a group having a π bond or a single bond (provided that at least one of R ₁ and R ₂ represents an electron-donating group, and R ₁ ′ and R ₂ And at least one of ′ represents an electron donating group. At least one of R ₂ , R ₃ and R ₄ represents a group having a π bond, and at least one of R ₂ ′, R ₃ ′ and R ₄ ′. One represents a group having a π bond) R ₅ and R ₅ ′ represent an aryl group having a quinoid structure or a double bond, and x, y, z ₁ and z ₂ are each 0 ≦ x < l00, 0 <y ≦ 100, 0 ≦ z ₁ <100, 0 ≦ z ₂ <100 and x + y + z ₁ + z ₂ = 10 (It is a natural number satisfying the equation of 0, and represents a numerical value indicating the polymerization ratio of the monomer.)

When the conjugated polymer compound represented by the general formula (V) serving as a precursor of the conjugated polymer compound of the present invention has two or more side chains having an ethynylene group, R ₆ can be a group having two or more side chains into which a cyano group is introduced. For example, when it has two side chains, general formula (I) can be represented as the following general formula (XVII).

(In the formula, R ₁ and R ₁ ′ represent a hydrogen atom, a group having a π bond, or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R _4. Represents a group having a π bond or a single bond (provided that at least one of R ₁ and R ₁ ′ or R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ is π R ₅ represents an aryl group having a quinoid structure or a double bond, and x, y, and z are 0 ≦ x <100, 0 <y <100, and 0 <z ≦, respectively. (It is a natural number satisfying the formula of 100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

  The conjugated polymer compound represented by the following general formula (V), which is a precursor of the conjugated polymer compound represented by the general formula (I) of the present invention, has an ethynylene group (carbon-carbon triple bond) on the side chain. It can be obtained by copolymerizing the monomer having and other monomers if necessary.

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₆ represents one or more monomer structural units composed of a group having a π bond, wherein x, y and z are 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and (It is a natural number satisfying the formula x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)

Here, the method of polymerizing the monomer is not limited to these, but for example, a method of polymerizing by a cross coupling reaction using a palladium / phosphorus catalyst, a method of polymerizing by a Sonogashira coupling reaction, Heck, Method of polymerizing by coupling reaction, method of polymerizing by Suzuki coupling reaction, method of polymerizing by Grignard reaction, sulfonium salt precursor method, Wittig-Horner reaction, Knoevenagel method, method of polymerizing by Ni (O) catalyst, FeCl ₃ A method of polymerizing with an oxidant such as a method, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like can be used.

In the general formula (V), R ₁ is a group having a π bond or an electron donating group, R ₂ is a phenyl group having a divalent amine at the para position, R ₃ is a single bond, R ₄ Is a group having a π bond and z = 0, and a method for synthesizing a compound represented by the following general formula (VII) will be described.

（式中、Ｒ_１は、π結合を有する基又は電子供与性基を表す。Ｒ_４は、π結合を有する基を表す。ｘ+ｙはモノマーが重合してポリマーとなっていることを表す。）

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X + y represents that a monomer is polymerized to form a polymer. .)

  The compound represented by the general formula (VII) is composed of a compound represented by the following general formula (VIII) and a compound represented by the following general formula (IX) as shown in the following reaction formula (3). Can be synthesized by cross coupling.

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X represents a halogen atom. X + y represents a monomer polymerized. (Indicates that it is a polymer.)

  In this reaction formula (3), it is preferable to use a coupling reaction by a palladium / phosphorus catalyst. That is, it can be cross-coupled in an organic solvent such as toluene in the presence of a palladium catalyst such as tris (dibenzylideneacetone) dipalladium and a phosphorus ligand such as tri (tert-butyl) phosphine.

  The conjugated polymer compound obtained by the general formula (VII) obtained by the above reaction is further added with tetracyanoethylene as shown in the following reaction formula (2) to give the following general formula (III) A conjugated polymer compound having a controlled electronic state can be produced.

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X and y are 0 ≦ x <100, 0 <y, respectively. ≦ 100 and x + y = 100 are natural numbers that satisfy the formulas and represent numerical values indicating the polymerization ratio of monomers.)

  Since the conjugated polymer compound of the present invention can control the electronic state and has a visible light absorption effect derived from intramolecular donor-acceptor interaction, it is used as a p-type semiconductor material for organic thin-film solar cells. Suitable for

The p-type semiconductor material of the present invention can be used by being dispersed in a solvent together with an n-type organic semiconductor. In order to reduce the viscosity and form a uniform coating film, it is preferable that the molecular weight of the p-type semiconductor material of the present invention is 5 million or less. As the n-type organic semiconductor, for example, fullerene derivatives, carbon nanotubes, polyphenylene vinylene, polyfluorene, derivatives thereof, and copolymers thereof can be used.
When the following PCBM, which is a fullerene derivative, is used as an n-type semiconductor, the conjugated polymer compound of the present invention in which the LUMO value is in the vicinity of 3.9 eV and the HOMO value is controlled in the vicinity of 5.4 eV is used. For example, a p-type semiconductor material can be used.

  The p-type semiconductor material of the present invention dispersed in a solvent together with the n-type organic semiconductor is coated on the first electrode layer formed on the substrate by a spin coat method, a die coat method, an ink jet method, or the like, can do. A second electrode can be further formed on the photoelectric conversion layer. The applied n-type organic semiconductor material and p-type semiconductor material undergo phase separation, and connect the electrodes as a hole and electron transport path, respectively, to form an organic thin film solar cell element as a whole.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to these Examples.

(Synthesis of a precursor conjugated polymer compound having an ethynylene group in the side chain)
The precursor polymer was synthesized by polycondensation between bifunctional monomers according to the route shown below.

After putting 100 mg of 4- (phenylethynyl) aniline and 284 mg of 2,7-dibromo-9,9-dioctylfluorene into the polymerization tube, 13.3 mg of tris (dibenzylideneacetone) dipalladium as a catalyst, tri (tert-butyl) phosphine 22 μL, sodium tert-butoxide 162 mg as a base, and toluene 0.60 mL as a solvent were added. After connecting to a vacuum line and sealing and degassing, the mixture was heated and stirred at 60 ^° C. for 24 hours. After cooling to room temperature, water and dichloromethane were added for liquid separation. The dichloromethane phase was dropped into methanol to obtain an aromatic polyamine condensate as a yellow powder.
Yield 60%, IR (3035, 2925, 2853, 2213, 1598, 1510, 1464, 1443, 1313, 1271, 1179, 1136, 1106, 1071, 820, 754, 690 cm ^-1 ), ¹ H NMR (0.85 -1.80 (m, alkyl), 6.78-7.62 (m, Ar)), number average molecular weight 4,300, weight average molecular weight 9,100, UV-visible absorption maximum 398 nm.

After 122 mg of 4-[(4-aminophenyl) ethynyl] -N, N-dimethylaniline and 284 mg of 2,7-dibromo-9,9-dioctylfluorene were placed in the polymerization tube, tris (dibenzylideneacetone) 13.3 mg of palladium, 22 μL of tri (tert-butyl) phosphine, 162 mg of sodium tert-butoxide as a base, and 0.60 mL of toluene as a solvent were added. After connecting to a vacuum line and sealing and degassing, the mixture was heated and stirred at 60 ^° C. for 24 hours. After cooling to room temperature, water and dichloromethane were added for liquid separation. The dichloromethane phase was dropped into methanol to obtain an aromatic polyamine condensate as a yellow powder.
Yield 70%, IR (3035, 2924, 2852, 2208, 1609, 1579, 1522, 1463, 1442, 1354, 1309, 1269, 1196, 1170, 1132, 946, 815, 720, 524 cm ^-1 ), ¹ 1 H NMR (0.87-1.80 (m, alkyl), 2.33 (s, Me), 6.34-7.65 (m, Ar)), number average molecular weight 13,300, weight average molecular weight 45,600, UV-visible absorption maximum 403 nm.

After putting 141 mg of 4-[(triisopropylsilyl) ethynyl] aniline and 284 mg of 2,7-dibromo-9,9-dioctylfluorene into the polymerization tube, 13.3 mg of tris (dibenzylideneacetone) dipalladium as a catalyst, tri (tert -Butyl) phosphine 22 μL, sodium tert-butoxide 162 mg as a base and toluene 0.60 mL as a solvent were added. After connecting to a vacuum line and sealing and degassing, the mixture was heated and stirred at 60 ^° C. for 24 hours. After cooling to room temperature, water and dichloromethane were added for liquid separation. Aromatic polyamine condensate as a yellow powder by dropping the dichloromethane phase into methanol (yield 37%, IR (3034, 2925, 2859, 2150, 1601, 1579, 1503, 1464, 1379, 1344, 1312, 1270, 1177 , 1105, 1073, 1015, 996, 919, 883, 832, 723, 678, 539 cm ^-1 ), ¹ H NMR (0.87-1.69 (m, alkyl), 1.14 (s, isopropyl), 6.78-7.45 (m , Ar)), a number average molecular weight 18,100, and a weight average molecular weight 110,000).
Further, 50 mg of this aromatic polyamine condensate was dissolved in 10 mL of THF, 0.15 mL of tetrabutylammonium fluoride solution (1M THF) was added, and the mixture was stirred at room temperature for 30 minutes. The THF solution was dropped into methanol to obtain an aromatic polyamine condensate having a triisoprosilyl group deprotected as a yellow powder.
Yield 99%, IR (3317, 2925, 2853, 2105, 1601, 1579, 1503, 1465, 1441, 1312, 1270, 1173, 1105, 818, 722, 645, 598 cm ^-1 ), ¹ H NMR (0.82 -1.75 (m, alkyl), 2.76 (s, C≡CH), 6.88-7.50 (m, Ar)), number average molecular weight 13,500, weight average molecular weight 55,700, UV-visible absorption maximum 391 nm.

(Addition of tetracyanoethylene)
The reaction with tetracyanoethylene was carried out according to the route shown below.

After dissolving 7.0 mg of alkyne-containing aromatic polyamine precursor in 1.0 mL of dichloroethane, 1.6 mg of tetracyanoethylene was added under a nitrogen atmosphere. After stirring at room temperature for 1 hour, the solvent was removed under reduced pressure to obtain the target tetracyanobutadiene structure-containing aromatic polyamine (conjugated polymer compound 1).
Yield 100%, IR (2925, 2854, 2220, 1721, 1596, 1558, 1543, 1490, 1464, 1440, 1332, 1282, 1259, 1202, 1181, 1126, 1073, 1040, 1008, 960, 921, 797 , 744, 690 cm ⁻¹ ), ¹ H NMR (0.85-1.85 (m, alkyl), 6.84-7.53 (m, Ar)), number average molecular weight 6,400, weight average molecular weight 9,900, UV-visible absorption maximum 522 nm.

Since this reaction is an addition reaction that does not generate a by-product, the yield can be easily calculated by quantifying the increase in the weight of the polymer. As a result of confirming the structure by NMR, it proceeded without side reaction as in the case of the low molecular weight compound, and thus a quantitative yield could be achieved.
In IR, the weak stretching vibration absorption 2213cm ^-1 derived from the precursor alkyne disappeared, and a very strong stretching vibration absorption derived from the cyano group appeared at 2220cm ^-1 newly. Further, when the UV-visible absorption spectrum was measured in dichloromethane, as shown in FIG. 1, the precursor had an absorption maximum of 398 nm, whereas the tetracyanoethylene adduct had a long wavelength shift to 522 nm. This is charge transfer absorption derived from intramolecular donor-acceptor interaction, which also proves that the target structure has been obtained.

Electrochemical measurement in room temperature dichloromethane (0.1M tetra-n-butylammonium perchlorate) revealed a clear difference between before and after the reaction of tetracyanoethylene, as shown in FIG.
Before the reaction, a reversible oxidation wave was observed from about 0.30 V (vs. Ag / Ag ⁺ ) to about 0.80 V, but no clear reduction wave derived from the sample was observed. However, after the reaction, a reversible oxidation wave was observed in the range of about 0.44 to 0.89V. In addition, a new irreversible reduction wave appeared at -0.85V. The shift of the oxidation potential of the aromatic amine polymer to the anode side after the reaction indicates that it interacts with the electron-attracting tetracyanobutadiene structure via a conjugated system in the molecule. Moreover, since the reduction potential of unsubstituted tetracyanobutadiene is estimated to be −0.31 V (vs. Fc ⁺ / Fc) (Non-patent Document 4, p. 1889), the reduction potential derived from the tetracyanobutadiene skeleton is also donated by electrons. It shifted to the cathode side by conjugating linking with a functional aromatic amine polymer.

This target polymer structure is also characterized in that it can be synthesized only by a polymer reaction between tetracyanoethylene and an electron-rich alkyne-containing polymer. That is, as shown below, it cannot be synthesized by polycondensation of a tetracyanobutadiene monomer that has been reacted with tetracyanoethylene in advance. In the monomer containing a cyano group, the reaction does not proceed because the Pd catalyst is coordinated to the cyano group. Another reason is that an amino group substituted with an electron-withdrawing group is less likely to cause a catalytic reaction because the electron density on nitrogen is reduced.

After dissolving 10 mg of alkyne-containing aromatic polyamine precursor in 5.0 mL of dichloroethane, 2.1 mg of tetracyanoethylene was added under a nitrogen atmosphere. After stirring at room temperature for 1 hour, the solvent was removed under reduced pressure to obtain the target tetracyanobutadiene structure-containing aromatic polyamine (conjugated polymer compound 2).
Yield 100%, IR (2925, 2853, 2218, 1605, 1490, 1464, 1440, 1384, 1347, 1318, 1270, 1177, 945, 820, 671 cm ^-1 ), ¹ H NMR (0.62-1.83 (m alkyl), 3.14 (s, Me), 6.67-7.77 (m, Ar))), number average molecular weight 14,400, weight average molecular weight 28,800, UV-visible absorption maximum 472 nm.

The weight average molecular weight calculated from GPC decreased after reaction with tetracyanoethylene. This is presumably because the hydrodynamic volume of the polymer decreased because there were many dipolar interactions between cyano groups in the molecule. When MALDI-TOF MS measurement (matrix: 2- (4-hydroxyphenylazo) benzoic acid) that can directly detect molecular weight was performed, many peaks in which the molecular weight of tetracyanoethylene was added to the precursor polymer were detected. It was judged that the target polymer was obtained. From IR, the alkyne stretching vibration of 2208 cm ^-1 disappeared, and a strong cyano group stretching vibration appeared at 2218 cm ^-1 . The UV-visible absorption 403 nm in the precursor dichloromethane was shifted to 472 nm long after the reaction with tetracyanoethylene, and there was indeed a charge transfer interaction in the molecule.
Further, in the electrochemical measurement, as shown in FIG. 3, a completely reversible reduction wave was observed and was stable even after repeated sweeps. This is because chemical stability is increased by introducing an electron-donating dimethylamino group at the end of the side chain.

(Synthesis of a conjugated polymer compound in which R ₁ is hydrogen)

After dissolving 8.0 mg of alkyne-containing aromatic polyamine precursor in 1.0 mL of THF, 2.0 mg of tetracyanoethylene was added under a nitrogen atmosphere. After stirring at room temperature for 1 hour, the solvent was removed under reduced pressure to obtain the target tetracyanobutadiene structure-containing aromatic polyamine (conjugated polymer compound 3).
Yield 100%, IR (2927, 2855, 2222, 2197, 1722, 1595, 1498, 1465, 1441, 1321, 1280, 1185, 1113, 1069, 1036, 957, 836, 748, 680, 621 cm ^-1 ) ¹ H NMR (0.94-1.93 (m, alkyl), 6.72-7.55 (m, Ar)), UV-visible absorption maximum 516 nm.

Chemical stability was reduced in polymers that did not have an aromatic ring at one end of the alkyne. In the dilute solution, the tetracyanobutadiene structure-containing polymer was stable, but once the solvent was removed under reduced pressure and solidified, a component that did not re-dissolve in the solvent at a certain ratio was generated. It is thought that an intermolecular reaction occurred at the 3-position active hydrogen site of the tetracyanobutadiene skeleton, resulting in an insoluble component. In the case of a low-molecular-like structure, it is a phenomenon unique to polymers because it is sufficiently stable even if it is solid.
The UV-visible absorption in the precursor dichloromethane was observed at 391 nm, but the dichloromethane soluble component after the reaction with tetracyanoethylene shifted to a long wavelength to 516 nm. In electrochemical measurements, the current value gradually increased with repeated sweeps, suggesting the possibility of adsorption and side reactions on the electrode surface.

Since the electronic state of the conjugated polymer compound of the present invention is controlled, the conjugated polymer compound is useful as an organic semiconductor used for an organic thin solar cell or the like.

It is a figure which shows the ultraviolet visible absorption spectrum in the conjugated polymer compound 1 before and after the tetracyanoethylene reaction. It is a figure which shows the electrochemical response behavior before and after the tetracyanoethylene reaction in the conjugated polymer compound 1. It is a figure which shows the electrochemical response behavior before and after the tetracyanoethylene reaction in the conjugated polymer compound 2.

Claims (20)

A conjugated polymer compound represented by the following general formula (I):

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.) 2. The conjugated polymer compound according to claim 1, wherein at least one of R ₁ and R ₂ is a phenyl group having an amine in at least one of a para position and an ortho position or a ferrocene-containing group which may have a substituent. A conjugated polymer compound, which is any electron donating group. 3. The conjugated polymer compound according to claim ₂ , wherein at least one of R ₁ and R ₂ is a phenyl group having an amine in at least one of a para position and an ortho position. 4. The conjugated polymer compound according to claim 3, wherein R ₂ is a phenyl group having an amine at the para position, and is represented by the following general formula (II):

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond, or an electron donating group. R ₃ and R ₄ represent a group having a π bond or a single bond, and at least of R ₃ and R ₄ One represents a group having a π bond, R ₅ represents an aryl group having a quinoid structure or a double bond, and R ₆ represents one or more monomer structural units each composed of a group having a π bond. X, y, and z are natural numbers that satisfy the following expressions: 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100, and x + y + z = 100, respectively, (Shows the numerical value shown.) The conjugated polymer compound according to claim 4, wherein R ₁ is a group having a π bond or an electron donating group. 6. The conjugated polymer compound according to claim 5, wherein R ₃ is a single bond, R ₄ is a group having a π bond, R ₅ is a double bond, and z is 0. And a conjugated polymer compound represented by the following general formula (III):

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X and y are 0 ≦ x <100, 0 <y ≦, respectively. (It is a natural number satisfying the equation of 100 and x + y = 100, and represents a numerical value indicating the polymerization ratio of the monomer.) The conjugated polymer compound according to claim 2, wherein R ₁ is a phenyl group having an amine in at least _one of a para position and an ortho position, and R ₂ is a group having a π bond. Conjugated polymer compounds. 2. The conjugated polymer compound according to claim 1, wherein R ₆ is two types of monomer structural units composed of a group having a π bond, and is represented by the following general formula (IV):

(In the formula, R ₁ and R ₁ ′ represent a hydrogen atom, a group having a π bond, or an electron donating group. R ₂ and R ₂ ′ represent an electron donating group or a group having a π bond, and R ₃ , R ₃ ′, R ₄ , and R ₄ ′ represent a group having a π bond or a single bond (provided that at least one of R ₁ and R ₂ represents an electron-donating group, and R ₁ ′ and R ₂ And at least one of ′ represents an electron donating group. At least one of R ₂ , R ₃ and R ₄ represents a group having a π bond, and at least one of R ₂ ′, R ₃ ′ and R ₄ ′. One represents a group having a π bond) R ₅ and R ₅ ′ represent an aryl group having a quinoid structure or a double bond, and x, y, z ₁ and z ₂ are each 0 ≦ x < l00, 0 <y ≦ 100, 0 ≦ z ₁ <100, 0 <z ₂ <100 and x + y + z ₁ + z ₂ = 10 (It is a natural number satisfying the equation of 0, and represents a numerical value indicating the polymerization ratio of the monomer.)   An electron-donating group is a phenyl group having an amine in at least one of the para-position and the ortho-position, a phenyl group having an alkoxy group in at least one of the para-position and the ortho-position, an amino group, a mono-substituted amino group, a di-substituted amino group, A ferrocene-containing group which may have a substituent, a thiophene-containing group which may have a substituent, a pyrrole-containing group which may have a substituent, and a carbazole which may have a substituent The conjugated polymer compound according to claim 1, wherein the conjugated polymer compound is an electron donating group selected from the group consisting of groups.   10. The conjugated polymer compound according to claim 9, wherein the electron donating group is a phenyl group having an amine at the para position or the ortho position.   A group having a π bond is thiophene, phenylene, phenylene vinylene, fluorene, phenylene ethynylene, vinylene, ethynylene, thiazole, benzodithiophene, thienothiophene, dithienothiophene, cyclopentadithiophene, triphenylamine, pyrrole, 2, The group according to any one of claims 1 to 10, which is a group containing one or more chemical structures selected from the group consisting of 1,3-benzothiadiazole, thienopyrazine and 1H-benzo [de] anthracene. Conjugated polymer compound.   The aryl group having a quinoid structure is a cyclohexa-2,5-diene-1,4-diylidene group, 2,3,5,6-tetrafluorohexa-2,5-diene-1,4-diylidene group, naphthalene The conjugated polymer according to any one of claims 1 to 5 and 7 to 11, which is a group selected from the group consisting of a -2,6-diylidene group and an anthracene-9,10-diylidene group. Compound. The following reaction to obtain the conjugated polymer compound represented by the following general formula (I) by reacting the conjugated polymer compound represented by the following general formula (V) with the compound represented by the following general formula (VI) The method for producing a conjugated polymer compound according to claim 1, comprising a step represented by formula (1).

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.) A conjugated polymer compound represented by the following general formula (III) is reacted with a tetracyanoethylene represented by the following general formula (A-1) to the conjugated polymer compound represented by the following general formula (VII). The method for producing a conjugated polymer compound according to claim 6, comprising a step represented by the following reaction formula (2):

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X and y are 0 ≦ x <100, 0 <y, respectively. ≦ 100 and x + y = 100 are natural numbers that satisfy the formulas and represent numerical values indicating the polymerization ratio of monomers.) 15. The production method according to claim 14, further comprising reacting a compound represented by the following general formula (VIII) with a compound represented by the following general formula (IX) to represent the following general formula (VII): A method for producing a conjugated polymer compound comprising a step represented by the following reaction formula (3) for synthesizing a conjugated polymer compound.

(In the formula, R ₁ represents a group having a π bond or an electron donating group. R ₄ represents a group having a π bond. X represents a halogen atom. X + y represents a monomer polymerized. (Indicates that it is a polymer.) The manufacturing method of the conjugated polymer compound characterized by including the process of following (A)-(C):
(A) By changing the abundance ratio of the conjugated polymer compound represented by the following general formula (V) and the compound represented by the following general formula (VI), a plurality of reactions represented by the following reaction formula (1) are performed. Process;
(B) Measurement of electronic state of a plurality of conjugated polymer compounds obtained by the step (A) represented by the following general formula (I) and having different ratios of x and y Performing steps;
(C) A step of selecting a conjugated polymer compound having a desired electronic state.

(In the formula, R ₁ represents a hydrogen atom, a group having a π bond or an electron donating group. R ₂ represents an electron donating group or a group having a π bond, and R ₃ and R ₄ represent a π bond. (Wherein at least one of R ₁ and R ₂ represents an electron donating group, and at least one of R ₂ , R ₃ and R ₄ represents a group having a π bond). R ₅ represents an aryl group or a double bond having a quinoid structure, R ₆ represents one or more monomer structural units composed of a group having a π bond, and x, y, and z are respectively (It is a natural number satisfying the formulas 0 ≦ x <100, 0 <y ≦ 100, 0 ≦ z <100 and x + y + z = 100, and represents a numerical value indicating the polymerization ratio of the monomer.)   The conjugated polymer compound having a HOMO level of 5.2 to 5.6 eV and a LUMO level of 3.7 to 4.1 eV is selected in the step (C). 16. A method for producing a conjugated polymer compound according to 16.   A conjugated polymer compound obtained by the production method according to claim 16.   The p-type conductive polymer material for organic thin-film solar cells containing the conjugated polymer compound in any one of Claims 1-12 and 18. An organic thin film solar cell element comprising: a first electrode layer; a photoelectric conversion layer containing the p-type conductive polymer material according to claim 19; and a second electrode layer.

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